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Carbon Dioxide and Methane Measurements from the Los Angeles Megacity Carbon Project: 1. Calibration, Urban Enhancements, and Uncertainty Estimates

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We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban scale CO2 and CH4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four "extra-urban" sites including: two "coastal/marine" sites, one "continental" site in the high desert northeast of LA, and one "continental/mid-troposphere" site located in the San Gabriel Mountains. We find that a local marine background can be established to within roughly 1 ppm CO2 and 10 ppb CH4 using these local measurement sites. We also show that continental sites may not be relevant for selecting background observations during summer months due to the prevalence of onshore flow, which could transport CO2 and CH4 from the LA Basin to relatively remote sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. "Urban" and "suburban" sites show moderate to large CO2 and CH4 enhancements relative to a marine background to estimate. An urban site near Downtown LA has a median enhancement of roughly 20 ppm CO2 and 150 ppb CH4 during all hours, and roughly 15 ppm CO2 and 80 ppb ΔCH4 during midday hours (roughly 12–16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO2 and 1 ppb CH4 based on the repeated standard gas measurements from the LA sites during the last 1–2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the observations being elevated relative to the single-point calibration method; however the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The approach to identifying background mole fractions described here results in uncertainty ranging from roughly 5 and 15 % of the enhancement near downtown LA for CO2 and CH4, respectively, during afternoon hours. Overall, analytical and background uncertainties are small relative to the local CO2 and CH4 enhancements, however, our results suggest that reducing the uncertainty to less than 5 % of the enhancement will require detailed assessment of the impact of meteorology on background conditions.
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1
Carbon Dioxide and Methane Measurements from the Los Angeles
Megacity Carbon Project: 1. Calibration, Urban Enhancements, and
Uncertainty Estimates
Kristal R. Verhulst1, Anna Karion2, Jooil Kim3, Peter K. Salameh3, Ralph F. Keeling3, Sally Newman4, 5
John Miller5,6, Christopher Sloop7, Thomas Pongetti1, Preeti Rao1, Clare Wong1,4,*, Francesca M.
Hopkins1, Vineet Yadav1, Ray F. Weiss3, Riley M. Duren1, and Charles E. Miller1
1NASA Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA
2National Institute of Standards and Technology (NIST), Gaithersburg, MD, USA 10
3Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA, USA
4Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California, USA
5NOAA/ESRL/GMD, Boulder, CO, USA
6CIRES, University of Colorado, Boulder, CO, USA
7Earth Networks, Inc., Germantown, MD, USA 15
*Now at: California State University, Northridge, Northridge, California, USA
Correspondence to: K. R. Verhulst (Kristal.R.Verhulst@jpl.nasa.gov)
Abstract. We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles
(LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air
masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban scale CO2 and CH4 20
measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban
environments globally. We estimate background mole fractions entering LA using observations from four “extra-urban” sites
including: two “coastal/marine” sites, one “continental” site in the high desert northeast of LA, and one “continental/mid-
tropospheresite located in the San Gabriel Mountains. We find that a local marine background can be established to within
roughly 1 ppm CO2 and 10 ppb CH4 using these local measurement sites. We also show that continental sites may not be 25
relevant for selecting background observations during summer months due to the prevalence of onshore flow, which could
transport CO2 and CH4 from the LA Basin to relatively remote sites. Overall, atmospheric carbon dioxide and methane levels
are highly variable across Los Angeles. “Urban” and “suburban” sites show moderate to large CO2 and CH4 enhancements
relative to a marine background to estimate. An urban site near Downtown LA has a median enhancement of roughly 20
ppm CO2 and 150 ppb CH4 during all hours, and roughly 15 ppm CO2 and 80 ppb CH4 during midday hours (roughly 12-30
16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is
typically better than 0.1 ppm CO2 and 1 ppb CH4 based on the repeated standard gas measurements from the LA sites during
the last 1-2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the
observations being elevated relative to the single-point calibration method; however the uncertainty in the background mole
fraction is much larger than the measurement uncertainty. The approach to identifying background mole fractions described 35
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
c
Author(s) 2016. CC-BY 3.0 License.
2
here results in uncertainty ranging from roughly 5 and 15% of the enhancement near downtown LA for CO2 and CH4,
respectively, during afternoon hours. Overall, analytical and background uncertainties are small relative to the local CO2 and
CH4 enhancements, however, our results suggest that reducing the uncertainty to less than 5% of the enhancement will
require detailed assessment of the impact of meteorology on background conditions.
1 Introduction 5
Improved understanding of carbon dioxide (CO2) and methane (CH4) emissions from cities has been identified as a
priority for both carbon cycle science and to support climate mitigation efforts (Hutyra et al., 2014; Pacala et al., 2011).
More than half of the global population currently resides within cities, with the fraction living in urban areas projected to
increase in the future (United Nations, 2014). Currently, more than 70% of anthropogenic greenhouse gases (GHG) are
emitted from cities globally (IEA, 2008). The combination of carefully designed urban-scale atmospheric CO2 and CH4
10
monitoring networks, tracer transport modelling, and functionally resolved emissions data sets has the potential to offer
significant advances in understanding and managing urban carbon emissions (Duren and Miller, 2012).
Carbon fluxes can be estimated using “top-down” or “bottom-up” methods. Both approaches are complementary to
one another and can be beneficial for informing policy. Top-down approaches typically attempt to estimate carbon sources
and sinks from measured patterns of variability based on atmospheric observations. By contrast, bottom-up methods require 15
an investigation of local processes and/or construction of models, such as combining fossil fuel usage data from each source
sector with estimates of the carbon content of the fuel type (Gurney et al., 2009, 2012). An integrated topdown approach
can be very useful, especially given the complex mixtures of anthropogenic and biogenic CO2 and CH4 sources found in
urban ecosystems, which may be difficult to quantify using bottomup methods (Duren and Miller, 2012; Hutyra et al.,
2014). Top-down measurements are also advantageous in that they can be reported with fully traceable and rigorously 20
defined uncertainties. In this way, measurement records with both high precision and long-term stability are crucial to the
objective evaluation of reported emissions at local, regional, and continental scales (roughly 102-106 km2; e.g. Andrews et
al., 2014).
In recent years, there has been growing international interest in using top down atmospheric approaches to quantify
urban GHG fluxes (e.g. Duren and Miller, 2012; McKain et al., 2012, 2015). Large, organized urban greenhouse gas 25
monitoring projects have emerged in many cities, including Paris (CO2-Megaparis: http://co2-megaparis.lsce.ipsl.fr; e.g.
Bréon et al., 2015; Xueref-Remy et al., 2016), Boston (McKain et al., 2015), Indianapolis (Influx: http://influx.psu.edu; e.g.
Turnbull et al., 2015), Salt Lake City (http://lair.utah.edu/page/project/uta/pilot/; e.g. McKain et al., 2012), and, in this study,
the Los Angeles Megacity (https://megacities.jpl.nasa.gov/portal/; see also Feng et al., 2016). To date, most of these
research efforts have been largely disconnected. More information flow between existing urban observational networks and 30
the science and applications communities is needed to understand greenhouse gas emissions from cities. The data and
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
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Author(s) 2016. CC-BY 3.0 License.
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methods for greenhouse gas monitoring in urban regions should be fully disclosed and documented with a small degree of
latency to make the best use of these atmospheric data for emissions verification and/or for informing policies more
generally.
The Megacities Carbon Project was established through a multi-agency and multi-institution collaboration to
develop and demonstrate policy-relevant carbon monitoring in some of the world’s largest and most complex cities, and to 5
help address gaps in our knowledge of greenhouse gas emissions (Duren and Miller, 2012, and
https://megacities.jpl.nasa.gov/portal/). The LA pilot project involves continuous and discrete flask sampling of air to
monitor greenhouse and trace gas concentrations, together with isotopic ratios of CO2 at multiple surface sites. This study
describes the Los Angeles surface measurement network. The LA project has dramatically expanded the number of
greenhouse gas observing sites in the South Coast Air Basin since 2013, allowing unprecedented spatio-temporal 10
measurement coverage in this region. In this study, we describe the Los Angeles Megacity surface network, sampling
strategy, and calibration methods. We also discuss some preliminary results on CO2 and CH4 enhancements in the LA Basin
and some detailed metrics for evaluating uncertainties in our observations.
The Los Angeles Megacity is home to >15 million residents and spans roughly 17,100 km2 in California’s South
Coast Air Basin (SCB, Figure 1). Observations from the LA network will also be useful for future assessment of GHG 15
emissions in the South Coast Air Basin, which encompasses more than 43% of the CA statewide population. Policies and
strategies for mitigation of CO2 and CH4 emissions are currently being implemented in California, with measures being
passed at the state and local levels. The California Global Warming Solutions Act of 2006 (AB 32) requires California to
reduce its GHG emissions to 1990 levels by 2020, a 15% reduction below emissions expected under a business-as-usual
scenario. 20
The SCB presents unique challenges in terms of the complexity of the land surface, meteorology, and spatial-
temporal variability of its CO2 and CH4 emissions. Urban and suburban areas in the SCB have high population densities and
a large variety of anthropogenic CO2 and CH4 emissions sources, as well as non-zero CO2 fluxes expected from the
terrestrial biosphere (Feng et al., 2016; Newman et al., 2013, 2016) and potential for CH4 from natural geologic seeps (e.g.
Peischl et al., 2013). The SCB is bordered by the Pacific Ocean to the west and by mountains to the north and east. The 25
mesoscale circulation patterns observed over the LA megacity are challenging to represent in atmospheric transport models
(e.g. Angevine et al., 2012; Conil and Hall, 2006; Feng et al., 2016). Complex topography within the Basin can allow
formation of micrometeorological zones, which may result in concomitant transport complexity. Prior studies suggest a
dense measurement network with a high-degree of spatial and temporal resolution is required to provide robust, spatially-
resolved greenhouse gas flux estimates for the Los Angeles megacity (Kort et al., 2013). 30
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
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Urban areas such as Los Angeles contain a complex mixture of sources. Urban CO2 emissions can originate from
both anthropogenic and biospheric processes. Urban anthropogenic CO2 sources mainly reflect fossil fuel usage (including
combustion of gasoline in cars and combustion of natural gas for electricity production, including seasonal cooling and
heating), while biospheric CO2 sources include photosynthesis and above- and below-ground respiration (Djuricin et al.,
2010; Hutyra et al., 2014). CH4 can be produced via biogenic and thermogenic processes. Biogenic CH4 is produced as a 5
result of microbial decomposition of organic matter under anaerobic conditions (e.g. due to waste disposal in landfills and
wastewater treatment plants), and is also produced via enteric fermentation in the gut of livestock and from manure.
Thermogenic CH4 is derived from natural geologic processes that produce fossil fuels, and therefore is naturally present in
fossil fuel deposits including coal beds, oil fields, and geologic seeps (Etiope and Ciccioli, 2009). Thermogenic CH4 can also
be emitted through intentional venting and fugitive leaks in the extraction, storage, refining, transport, and use of natural gas, 10
as well as from incomplete combustion of fossil fuels.
In the LA Basin, many anthropogenic sources of CO2 and CH4 are co-located with each other and with potential
natural sources. LA is a major industrial and shipping hub, with a dense network of roads and freeways for transport, the Port
of Los Angeles, the Los Angeles International Airport, and also has extensive oil drilling infrastructure, with more than 10
local oil refineries and storage facilities. The LA Basin is also known for its naturally occurring geologic seeps, such as the 15
La Brea Tar Pits. In addition to extensive natural gas pipeline networks, LA also has a variety of other CH4 sources,
including landfills, wastewater treatment plants, fossil fuel extraction and refining, natural gas storage facilities, compressor
stations, and vehicle-fueling stations, and dairy agriculture, all of which can result in fugitive emissions (e.g. Hopkins et al.,
2016; Peischl et al., 2013; Viatte et al., 2016; Wennberg et al., 2012). The complex mixture of sources and intense human
impacts of urbanization complicate CO2 and CH4 source attribution in the LA Basin. 20
Several previous efforts have been made to characterize CO2 and CH4 in LA using in situ and remote sensing
observations. Some of the earliest published measurements of CO2 in Los Angeles date back to the 1970s (Newman et al.,
2008). Since then, there have been numerous studies investigating atmospheric CO2 and CH4 in the LA Basin using in situ
observations, including continuous and flask-based sampling from Mt Wilson (MWO; Hsu et al., 2010; Wennberg et al.,
2012), Pasadena (CIT) and Palos Verdes Peninsula (PVP; Newman et al., 2008, 2013, 2016), and remote-sensing studies, 25
including ground-based and space-based measurements (Kort et al., 2012; Viatte et al., 2016; Wong et al., 2015, 2016,
Wunch et al., 2009, 2016). Periodic intensive field campaigns using aircraft have allowed brief "snap-shot" assessments
(days to weeks in duration) of CO2 and CH4 levels and emissions in LA, including the campaigns ARCTAS-CA in 2008
(Jacob et al., 2010) and CalNex-LA in 2010 (Brioude et al., 2013; Cui et al., 2015; Peischl et al., 2013; Ryerson et al., 2013),
which were major field studies involving collaboration between the California Air Resources Board (ARB) and several 30
partner agencies to improve the accuracy of emissions inventories for greenhouse gases and atmospheric pollutants, as well
as a smaller, more recent campaign (Conley et al., 2016).
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
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Published: 4 October 2016
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Prior studies have consistently reported robust enhancements of CO2 (e.g. 30100 ppm CO2 at the surface and
roughly 28 ppm XCO2 column averaged dry-air mole fraction) and CH4 (e.g. 10’s to 100’s of ppb CH4 at the surface and
roughly 0.2-50 ppb XCH4 column averaged dry-air mole fraction), with significant temporal variability of the signals (Kort
et al., 2012; Newman et al., 2013, 2016; Viatte et al., 2016; Wecht et al., 2014; Wennberg et al., 2012; Wong et al., 2015;
Wunch et al., 2009). For CO2, radiocarbon (14C) isotopic tracer measurements have also been made at a limited number of 5
sites in Southern California (Djuricin et al., 2010, 2012, Newman et al., 2013, 2016; Riley et al., 2008). Djuricin et al. (2010)
demonstrated that fossil fuel combustion contributed up to 50-70% to CO2 sources during winter, while aboveground
biological respiration was found to contribute more CO2 than other sources during spring, when fossil fuel contributions
were smaller. Recently, Newman et al. (2016) determined that fossil fuel combustion is the dominant source of CO2 for
inland Pasadena using three-isotope approach, using 14C along with 13C and 18O stable isotopes, similar to Djuricin et al., 10
(2010). For CH4, emissions estimates based on top down methods indicate that bottom-up methods systematically
underestimate CH4 emissions in the LA megacity by roughly 30% to >100% (Cui et al., 2015; Jeong et al., 2013; Peischl et
al., 2013; Wecht et al., 2014; Wennberg et al., 2012; Wong et al., 2015, 2016; Wunch et al., 2009). Recent evidence from
stable isotopes of CH4 and light alkanes (e.g., ethane, propane, and butane) suggest that fossil emissions are the predominant
source of CH4 (Hopkins et al., 2016; Peischl et al., 2013; Wennberg et al., 2012; Townsend-Small et al., 2012), particularly 15
leakage from natural gas infrastructure and from local fossil CH4 sources.
In contrast to some of these earlier studies, the monitoring network described here provides near-continuous and
systematic monitoring of in situ CO2 and CH4 levels (as well as CO, which is not discussed in this work) at multiple sites in
the LA metropolitan area. The LA network allows continuous spatial and temporal measurement coverage at multiple sites,
spanning multiple years, which can be used in future top-down atmospheric inversion studies. The first part of this study 20
focuses on the sampling strategy and calibration method (Section 2). Next, we estimate hourly average CO2 and CH4 mole
fractions (Section 3) and discuss observation-based selection criteria for determining the background CO2 and CH4 mole
fractions using data from "extra-urban" sites (Section 4). One important result from this analysis is the near equivalence of
continental and marine boundary layer background estimates for this region. We then use a marine background estimate to
calculate urban CO2 and CH4 enhancements from the LA surface network during afternoon hours, the typical period of focus 25
for atmospheric flux inversions (Section 5). We also present a framework for estimating detailed time-dependent
uncertainties in the enhancement based on the combined uncertainty in the air sample data collected from the measurement
system and the background estimate (Section 6). We also compare data collected from analyzers in the field and independent
data collected at the NOAA/ESRL and Scripps Institution of Oceanography laboratories to estimate measurement
uncertainties. In addition to providing a foundation for subsequent flux studies for LA, the sampling strategy, calibration 30
methods, and uncertainty calculations described here are intended to be extensible to other surface observation networks in
complex cities around the world.
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
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Published: 4 October 2016
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2 Methods
2.1 Site selection criteria
The Los Angeles network design strategy began with a preliminary analysis based on a network receptor footprint
sensitivity analysis using WRF-STILT (Kort et al., 2013) and Vulcan (Gurney et al., 2009, 2012), which found that a
minimum of eight optimally located in-city surface observation sites were required for accurate monitoring of fossil fuel CO2
5
emissions in the LA megacity. Such a network was estimated to distinguish fluxes to within approximately 12 g C m-2 d-1
(roughly 10% of average peak fossil CO2 flux in the LA domain) on 8-week time scales and 10 km spatial scales (Kort et al.,
2013). We initially assessed the logistics of deploying instruments at or near each of the locations specified by Kort et al.
(2013). Site evaluation and siting criteria involved one or more of the following steps: (1) visual inspection of maps and
satellite imagery to investigate whether suitably tall structures were available and to assess potential impacts of terrain and 10
nearby strong greenhouse gas emission sources; (2) on-site surveys; (3) mobile measurement surveys in the region of interest
(Hopkins et al., 2016); and/or (4) short-term deployment of a continuous CRDS analyzer on a short tower (approx. 10 m) for
roughly 1-2 weeks prior to more permanent, fixed installation.
Where possible, measurement locations were sought on open-lattice communications towers. These structures were
favored as they tend to reduce the influence of perturbed airflow from the supporting structure itself and remote locations 15
minimize the influence of nearby emissions (Prasad et al., 2013). In the SCB, access to tall towers (>100 meters above
ground level) was limited to the surrounding mountain ranges, which would present unique complexities for modelling and
interpretation of the data. Therefore, towers within the Basin were limited to shorter cellular tower sites (<60 m), where
available. Although there are a large number of shorter cellular towers in the SCB, these structures were often inaccessible
due permitting or other restrictions. When no tower sites were available in a critical sampling area, we sought secure 20
locations on the rooftops of tall, multi-story buildings in the area of interest. The siting criteria and sampling design
framework were based on recommendations from Prasad et al. (2013) and McKain et al. (2015). In cases where rooftop sites
were evaluated, Large Eddy Simulations were performed to study the impact of recirculation and nearby structures on the
flow field around a building rooftop (Prasad et al., 2013).
2.2 Sampling locations 25
We established a network of eleven new surface observation sites distributed throughout three counties in the SCB
(Figure 1). The geographic coordinates, inlet heights, species measured, and installation dates are summarized in Table 1.
The tower sites include: Compton (COM), Granada Hills (GRA), Ontario (ONT), Victorville (VIC), and San Clemente
Island (SCI). The building/rooftop sites are all located on university campuses in the following cities: Los Angeles (USC,
University of Southern California), Pasadena (CIT, California Institute of Technology), Fullerton (FUL, California State 30
University Fullerton), and Irvine (UCI, University of California, Irvine). The La Jolla site (LJO) is located on Scripps pier,
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
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near a flask sampling location that has been discussed previously in the literature (e.g. Graven et al., 2012). The Palos
Verdes Peninsula (PVP) and Pasadena (CIT) measurements have been described previously in the literature, but are not
discussed in this study (Newman et al., 2013, 2016).
The measurement methods discussed below apply to the eleven new observation sites discussed here. All are
equipped with similar instrumentation and use an internally consistent sampling protocol and calibration strategy (see 5
Section 2.3-2.4). The LJO, SCI, VIC, and MWO sites are located outside the SCB boundary and are considered here as
“extra-urban” sites, which can be used to estimate background or boundary condition for the SCB (Figure 1). We use an
observation-based method to select background mole fractions from “extra-urban” sites, in part due to their remote locations
(see Sections 3 and 4 for further discussion).
2.3 Instrumentation 10
The Los Angeles Megacity greenhouse gas-monitoring network utilizes wavelength-scanned cavity ring-down
spectroscopy (CRDS) instruments (Picarro Inc., series G2301 and G2401; Rella et al., 2013; Welp et al., 2013) . All the
CRDS instruments measure CO2, CH4, and water vapor, while sites with Picarro G2401 instruments also measure CO (Table
1). There are 3 standard configurations for the sites discussed in this study: 1) towers with a single inlet height, 2) towers
with multiple inlet heights, and 3) rooftop sites, which follow a 4-corner sampling strategy. Table 1 also indicates the site 15
type, number of air inlets, and approximate heights for the air inlets. Air inlet heights vary from 13 to 100 meters above
ground level (m agl) for tower sites, and from 20 to 55 m agl for the rooftop sites. Many of the measurement sites discussed
in this study were installed, maintained, and/or operated by Earth Networks (EN, Germantown, MD,
https://www.earthnetworks.com/).
The gas-handling configuration for the EN greenhouse gas monitoring stations is shown in the Appendix (Figure 20
A1, adapted from Welp et al., 2013). The Earth Networks Sample Module houses a Valco 8-port low-pressure, dead-end
flow path selector with standard bore size of 0.75 mm (VICI, Valco Instruments Co. Inc., http://vici.com/vval/sd.php),
housed inside a heated box. The selector valve determines the sample type entering the CRDS cell (either outside air or
standard/calibration gases).
All tower and rooftop sites are equipped with EN meteorological stations (Weatherbug, Inc., 25
http://download.aws.com/manuals/RedBugBoxInstall.pdf), which measure wind speed, wind direction, ambient pressure,
ambient temperature, humidity, dew point temperature, and incident solar radiation. Rain gauges are installed below the gas
inlets. For tower sites, the wind measurements are co-located with the uppermost air inlet for the in situ greenhouse gas
analyzers. For rooftops, the air inlets and wind sensors are installed on the four corners of the building, with masts typically
positioned roughly 3-5 m above the roofline and roughly 90 degrees from the walls or edge of the building’s rooftop. Co-30
located meteorological measurements will allow better determination of the sensitivity of rooftop sites to local and regional
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
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emissions (i.e. when the winds are stronger or more consistent), relative to potential emissions from the building itself (i.e.
when the winds are calm).
The EN sample modules used in the LA surface network include a Nafion dryer housed in a thermostatic box (see
Figure A1 and description by Welp et al., 2013). The drying system consists of a 183 cm (72-inch)-long Nafion membrane
dryer (PermaPure, Inc., model MD-050-72S-1). An MKS640 pressure controller maintains a constant pressure to the Nafion 5
dryer during routine sampling of ambient air and calibration gases (set point roughly 800 mb, 600 Torr). Both sample air and
reference gases pass through a Nafion dryer before entering the CRDS cavity (see Appendix, Figure A1). The water vapor
concentrations in the sample and standard gases are roughly 0.1±0.01% H2O after passing through the Nafion dryer. The
analyzer pump redirects roughly 30% of the dry gas exiting the Nafion to the outer shell side of the dryer. Welp et al. (2013)
provide further discussion the design, testing, and implementation of this drying inlet system. Both the sample air and 10
reference gases are delivered to the Nafion at the same pressure in order to reduce the drying bias due to permeation through
the Nafion during routine operation, based on recommendations from Welp et al. (2013). The CRDS water vapor correction
and uncertainty due to the treatment of water vapor are described in more detail in Section 6.
Before each analyzer was deployed, the Picarro factory default orifice (O’Keefe A-18-NY) was replaced with a
smaller one (O’Keefe A-9-NY) to reduce the flow to about 70 sccm (cm3/minute at STP). A second critical orifice (O’Keefe 15
A-6-NY) was installed downstream of the Nafion to reduce the counterflow rate to about 30 sccm, and filters were added
upstream of the critical orifice to prevent particles from disrupting the flow. A separate small pump (ALITA AL-6SA Air
pump) module is installed for each air inlet and delivers a constant stream of sample air at 10 standard liters per minute
(sL/min) to the EN sample module. The air inlets consist of 9.525 mm (3/8”) Synflex tubing and an air intake filter
consisting of either a stainless steel or titanium wire mesh screen (100 Mesh SS or Monel mesh). 20
The CRDS analyzers communicate data directly with a Linux mini-computer on-site that receives the data stream
through a TCP connection. The site computer runs software (GCWerks, http://www.gcwerks.com), which controls the port
sampling sequence in the EN sample module. The software acquires all the high-frequency data points from the CRDS (i.e.
roughly 2.5 second time interval), EN sample module, and weather stations at each site, records extensive engineering data.
GCWerks also sends out pre-programmed email alarms so that instrument issues can be diagnosed remotely. All high-25
resolution data (Level 0 data) are retained. The GCWerks software then applies some basic automated quality control flags
and filters to the Level 0 data (the uncorrected, roughly 2.5 second resolution CRDS reading) and also rejects some data
points to create higher-level data products (see Appendix A1 and Table A1).
2.4 Calibration gases and sampling
Each measurement site is equipped with two natural air standard gas tanks that are calibrated on the World 30
Meteorological Organization (WMO) scales for CO2 and CH4. In the field, Parker Veriflo regulators (p/n: 45100653, Model:
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Published: 4 October 2016
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95930S4PV3304) are used to deliver gas from the calibration tanks, and are connected to the Earth Networks sample module
via 0.16 cm O.D. (1/16”) SS tubing. Field standards are prepared by the National Oceanic and Atmospheric Administration
Earth System Research Laboratory (NOAA/ESRL) and/or Scripps Institute of Oceanography (SIO) laboratory and are
calibrated relative to WMO scales before and after deployment in the field. The NOAA/ESRL ambient-level standards are
natural air tanks filled at Niwot Ridge, Colorado and calibrated against standards on the WMO-scale maintained by 5
NOAA/ESRL (X2007 for CO2, X2004A for CH4, http://www.esrl.noaa.gov/gmd/ccl/; (Dlugokencky, 2005; Zhao and Tans,
2006). For all standard tanks, we retrieve the most recent tank assignments from the NOAA Central Calibration Laboratory
(http://www.esrl.noaa.gov/gmd/ccl/refgas.html). The SIO standards are filled using a similar procedure, except tanks are
filled with natural coastal air from Scripps Pier in La Jolla, California. All mole fractions are reported in units of µmol gas
per mol dry air (ppm) or nmol gas per mol dry air (ppb). Both ambient-level tanks have mole fractions close to clean-air 10
ambient conditions (roughly 400 ppm CO2 and 1850 ppb CH4). Our calibration strategy ensures compatibility within the LA
surface network, and with other global atmospheric observations tied to the WMO scales.
The current calibration strategy for the LA surface network relies on a single-point calibration, tied to the
WMO/NOAA scale. One of the near-ambient tanks is assigned as the calibration standard, and the other tank is a target
standard, which is treated as an unknown sample. This calibration framework has been used extensively for calibration of 15
gas chromatography (GC-MS) instruments in remote monitoring networks, such as the ALE/GAGE/AGAGE network (e.g.
Prinn et al., 2001). The details of the calibration gas composition will be discussed in a separate publication
The CRDS analyzer samples each standard tank approximately every 22 hours (i.e. approximately daily). The target
tank measurement is staggered roughly 8-12 hours after the calibration gas (as well as the high mole fraction tank, where
applicable). All tanks are sampled for 20 minutes. The first 10 minutes of each tank run are rejected and only the data from 20
the last 10 minutes of any are used in the calibration of CO2 and CH4 mole fractions (Welp et al., 2013). Variations in the
measured target values and deviations from the assigned values are used to track the performance of the analyzer over time
and determine uncertainties for the air data (Section 6.1).
The instrument sensitivity (S) is calculated for each standard tank (the calibration tank, the target tank, and the high
mole fraction tank) and is determined as the ratio between the uncorrected CRDS reading and the tank’s assigned value on 25
the WMO scales (Xassigncal):
S = X'cal / Xassigncal (1)
where X’cal is the uncorrected CRDS reading (the dry mole fraction of the species of interest, in units ppm or ppb for CO2
and CH4, respectively). The sensitivity of the calibration tank is used to correct the air sample data, as described below.
Sensitivities for the target tank (and high-concentration tank, where available) are also tracked over time, however these 30
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tanks are not used in the calibration of the air data.
The CRDS analyzer provides a nominal mole fraction value, which we take as an uncalibrated measurement. We
then calibrate the uncorrected dry air sample mole fraction readings from the CRDS analyzer (X’air) using the single point
drift-correction method:
Xcorr = X'air * (Xassigncal / X'cal) (2) 5
= X'air / S
where Xcorr is the calibrated air data, X’cal is the dry mole fraction measurement of the calibration tank, and Xassigncal is the
assigned value of the calibration standard on the WMO scales (which is constant in time). For each instrument, we
interpolate the daily runs of the field calibration gas standard in time to provide a time stamp for X’cal at the time of the air
sample measurement. The units of Xcorr are in ppm CO2 or ppb CH4. 10
In addition to the ambient-level calibration and target tanks, the VIC and LJO sites had high mole-fraction standard
tanks installed at the time of this study. These tanks were prepared by NOAA/ESRL and calibration assignments were
provided prior to deployment (roughly 500 ppm CO2 and 2600 ppb CH4). We treat the high mole-fraction tanks as an
unknown target tank. The sensitivity (S) of the high mole fraction tank is also tracked over time, providing a check on the
analyzer stability at higher mole fractions. We use the high mole fraction tanks at these sites to estimate the uncertainty 15
associated with our single-point calibration strategy by calculating the residual of repeated measurement of the high mole
fraction tank from its assigned value. In Section 6.1 we discuss the individual components of uncertainty in the air
measurements, including the extrapolation uncertainty, which is the uncertainty due to our assumption that S is not
dependent on the mole fraction (see Section 6.1.1). In Appendix A2, we discuss an "Alternative calibration method" using
limited measurements of a high mole fraction tank installed at the La Jolla (LJO) and Victorville (VIC) sites in 2016. 20
3 Results
3.1 CO2 and CH4 observations
Atmospheric CO2 and CH4 mole fractions can vary on timescales ranging from less than 1 hour, to annual, and
inter-annual cycles. Figure 2 shows the 1 hour average observations collected from nine sites in the surface network
between January 1, 2013 and December 31, 2015. 25
Generally, each site exhibits the expected seasonal cycle for CO2 and CH4, with wintertime maxima and
summertime minima. The Downtown LA (USC), Compton (COM), and Fullerton (FUL) sites exhibit the highest average
CO2 levels during 2015 (Table 2). The annual average level was 421.6±17.5 ppm (USC, mean±1σ S.D.), 418.6±14.9 (FUL),
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and 418.0±16.9 ppm CO2 (COM) during afternoon hours (midday, roughly 12-16:00 LT or UTC-8, with no local adjustment
for daylight savings time). On average, the same three sites showed the highest average CH4 levels during 2015, in addition
to the “suburban” Granada Hills site (GRA). During afternoon hours, the annual average CH4 level was 2009.9±116.4 ppb
(USC), 1985.6±130.5 ppb (GRA) 1978.2±100.2 ppb (FUL) and 1977.2±109.8 ppb CH4 (COM). While USC exhibits the
highest levels of both gases, CH4 exhibits a somewhat different spatial pattern relative to CO2, with the GRA site showing 5
the second largest CH4 enhancements during midday. Overall the maximum 1 hour average measurement during afternoon
hours was 558 ppm CO2 and 3568 ppb CH4 at the COM and GRA sites, respectively (Figure 2 and Tables 2 and 3).
Victorville and San Clemente Island (VIC and SCI) show less variability in their annual average CO2 and CH4
levels compared to the other sites that are within the South Coast Air Basin (Figure 1). During 2015, CO2 levels at SCI
ranged from 391.2-425.2 ppm CO2, with an average level of 402.4±4.4 ppm CO2 during mid-afternoon hours. During mid-10
afternoon hours, CH4 levels ranged from 1824.7-2231.4 ppm CH4, with an average of 1900.9±37.9 ppb CH4. At VIC, CO2
levels at midday ranged from 395.9-442.6 ppm CO2, with an average of 404.5±3.7 ppm CO2, while CH4 levels ranged from
1832.7-2105.3 ppb CH4, with an average of 1898.6±32.9 ppb CH4. We find that SCI and VIC are the cleanest sites in terms
of their annual CO2 and CH4 variability. Feng et al. (2016) used a forward modelling framework to explore variability in
modelled CO2 mole fractions during the CalNex period (May-June 2010). Their results based on modelled CO2 “pseudo-15
data” are generally in agreement with the observations from these two “extra domain” sites. A third extra domain site is
located outside the SCB boundary, at La Jolla (LJO). On average, LJO appears to have more variability and higher CO2 and
CH4 levels compared to the SCI and VIC sites. The LJO site is outside the innermost model domain used Feng et al. (2016)
and was not discussed in that study.
The annual average CO2 variability observed at the IRV site is in the same range as other suburban sites, such as 20
GRA and FUL, based on the 2015 observation record. This result is somewhat in contrast with a result presented by Feng et
al., (2016), which showed IRV was a relatively clean site with respect to CO2 using pseudo-data. Although both IRV and
LJO are suburban sites and somewhat near the coast, on average, the CO2 and CH4 levels at LJO are typically lower than at
IRV. We note that differing prevailing meteorological conditions during spring/summer months compared to the rest of the
year could influence the CO2 and CH4 observations, especially for coastal sites such as IRV and LJO. These sites typically 25
exhibit less CO2 and CH4 variability during spring/summer when onshore flow may be stronger or more consistent. This
may explain the difference between our results and those reported by Feng et al., (2016).
The heterogeneous mixture of sources in urban LA complicates sectoral attribution of CO2 and CH4 sources. The
variability at each site is likely a reflection of the site’s footprint, or its sensitivity to sources in the area. Measurement
footprints are typically variable and generally larger during the daytime than at night, and as such footprints are also more 30
difficult to quantify during stable night-time conditions (Djuricin et al., 2010; Turnbull et al., 2015). Tables 2 and 3 show the
median and interquartile ranges for the CO2 and CH4 observations, respectively. At most sites, the data distributions are
skewed and have long-tails, where a relatively small fraction of observations exhibit significantly elevated CO2 and/or CH4
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levels (see also Section 5, where we discuss the long-tail distribution with regards to the enhancement above background).
Generally, high concentration spikes can occur at night and in the early morning, when the atmosphere is more stable, and
when the site is more sensitive to nearby sources. One example is the suburban GRA site, which shows many high
concentration CH4 spikes since data collection began in 2013 (Figure 2, right panels, note scale difference on the y-axis).
Many of the CH4 spikes throughout the GRA record occur at night, suggesting contributions from a nearby source that the 5
other measurement sites are not sensitive to. In general, we do not expect the surface sites to be equally sensitive to CO2 and
CH4, as the network design was only optimized for detection of fossil-fuel CO2 emissions (Kort et al., 2013). Resolving the
fine-scale structure of CO2 and CH4 emissions at the sectoral level will likely require footprint analysis and additional tracer
measurements, which are planned as part of future work.
In addition to emissions, it has been demonstrated previously that meteorology plays an important role in 10
controlling the variability of CO2 (and CH4) observations within the planetary boundary layer (e.g. Feng et al., 2016;
Newman et al., 2013; Xueref-Remy et al., 2016). Diurnal variations are driven in part by changes in the height of the PBL.
Newman et al. (2013) demonstrated this for CO2 using observations from the CIT site. A stable PBL prevents surface
emissions from mixing with the atmosphere above. Therefore, given a constant flux, the CO2 and CH4 mole fraction
observed within the PBL will increase or decrease as the PBL height falls or rises, respectively. Observations from midday 15
hours show less variance in the within-hour CO2 and CH4 values and a smaller inter-quartile range relative to all hours
(Table 2). The reduced variability in the CO2 and CH4 observations during midday hours is in part due to the stability of the
PBL depth during the mid/late afternoon. Rahn and Mitchell (2016) evaluated Aircraft Meteorological Data Relay
(AMDAR) automated weather reports from three major international airports in Southern California (LA, Ontario, and San
Diego) between 2001 and 2014. Overall, they found that PBL depth observations from LA (in the western LA Basin) 20
showed the least variability (smallest interquartile range) during the hours just before sunset (~21:00 UTC to 03:00 UTC)
indicating a fairly regular range of boundary layer height at this time (Rahn and Mitchell, 2016). CO2 and CH4 observations
are also more likely to be sensitive to local sources when the PBL is shallow and the atmosphere is less well mixed (and at
low wind speeds). The stability of the PBL height may also vary with season. Southern California is characterized by a well-
defined boundary layer during the spring and summer months due to strong temperature inversions associated with large-25
scale subsidence. During the autumn and winter, the large-scale subsidence is less prominent and the presence of a weak
temperature inversion (or one that extends down to near the surface) makes it more difficult to identify a boundary layer
(Rahn and Mitchell 2016). As part of future work, we plan to evaluate the diurnal and seasonal variability in the CO2 and
CH4 signals with PBL depth measurements from a mini micropulse lidar instrument installed near the location of the CIT
measurement site (Ware et al., 2016). 30
Wind speed is also an important factor controlling variability in observed CO2 (and CH4) mole fractions, as has
been demonstrated previously for CO2 (e.g. Newman et al., 2013; Xueref-Remy et al., 2016). This is also related to the
measurement footprint, as discussed earlier. For example, at low wind speeds, observations within the PBL are more likely
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to reflect sources and sinks in close proximity to the site (with distances of roughly 10 km or less), while at higher wind
speeds, the observation site will become more sensitive to transported emissions from more distant sources (d ~ 10-100 km),
while the influences from nearby sources will appear more diluted. We do not go into further detail on the impacts of
meteorology on the CO2 and CH4 signals as part of this analysis. Future work will explore the impacts of meteorology and
PBL height on the CO2 and CH4 (and CO) signals observed by the network using footprint analysis, and weather reanalysis 5
products.
There are three potential signals of interest for urban and regional greenhouse gas studies. All may be potentially
relevant for utilizing greenhouse gas measurements in local or regional inverse modelling studies: (1) diurnal changes in the
measured mole fraction at one location over a 24-hour period; (2) gradients in the measured mole fraction between locations;
and (3) the local enhancement (referred to here as ΔCO2 and ΔCH4), which is the difference between an observed mole 10
fraction at one location and an defined background mole fraction. In the remainder of this paper, we focus on the third type
of signal discussed above, the enhancement above background.
3.2 Calculating CO2 and CH4 enhancements
The enhancement relative to the background mole fraction can be useful for evaluating local additions of CO2 and
CH4 from urban regions. We define the enhancement or excess signal (ΔX) as follows: 15
ΔX = XOBS – XBG (3)
where XOBS is the calibrated CO2 or CH4 mixing ratio at the site of interest, XBG is the background mole fraction (i.e. the mole
fraction from an air mass entering the domain or region of interest), all with units of ppm CO2 or ppb CH4.
4 Estimating background mole fractions
A critical goal for the LA Megacity Carbon Project is to identify an optimized background measurement location 20
(or locations). Prior studies in the LA region have used either a coastal marine boundary layer background derived from
observations from La Jolla, CA (32.87°N; 117.25°W, 0 m asl; Graven et al., 2012), or Palos Verdes Peninsula (33.74 °N;
118.35°W, 116 m asl; Newman et al., 2013, 2016), or a continental, free-troposphere background based on night-time flask
measurements from the mountaintop site at Mt Wilson, CA in the San Gabriel mountains bordering the northern edge of the
LA Basin (MWO, 34.22°N; 118.06°W, 1670 m asl; Figure 1). Prior studies attempting to constrain CH4 emissions in 25
California have also estimated background mixing ratios along their model domain boundary using particle trajectory
endpoints from WRF-STILT footprint simulations as a look-up for a latitudinally averaged, 3-D marine boundary layer
(MBL) “curtain” product (Jeong et al., 2012, 2013; Zhao et al., 2009).
Evaluating the composition of a background air mass depends in part on the application. For example, in forward
and inverse modelling studies, the location and scale of the domain of interest will determine the background requirements. 30
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A model that is used to estimate the enhancement due to local emissions should account for influences from sources both
within and outside the domain of interest, as well as recirculation effects (i.e. when air exits the domain and returns a short
while later). There is obviously no single background that is representative for all cases. There may also be cases when a
single background site is not appropriate for estimating enhancements throughout the Basin. Out-of-domain sites may help
resolve within-domain emissions under some conditions, however the appropriate background site will also depend on the 5
prevailing meteorological conditions. For Los Angeles, if the prevailing wind is from the land (offshore), then a continental
background may be most appropriate, whereas if the wind is from the western coastal boundary (onshore), then a marine
background may be most appropriate. Out-of-domain influences can also lead to spatial gradients that are independent of
within-domain emissions, and will be more difficult to discern or characterize. In such cases, within domain sites may
occasionally be useful for characterizing background conditions. 10
In this study, the domain of interest is defined by the South Coast Air Basin boundary (Figure 1). The sites most
suitable for characterizing background (or upwind) conditions are SCI, LJO, VIC, and MWO, which are all located outside
this SCB domain. Overall, SCI, VIC, and LJO are most similar to the mole fractions of the remote MBL in terms of their
annual average CO2 and CH4 mole fractions (Table 2). LJO is a coastal, suburban site in La Jolla, CA (as described above);
SCI is an offshore island site located on San Clemente Island, CA, just southwest of LA (32.92°N; 118.49°W, 480 m asl). 15
VIC is a rural, desert site located outside the city of Victorville, CA (34.61°N; 117.29°W, 1370 m asl); and MWO is a
mountaintop site, as described above. LJO and SCI are potentially useful for characterizing the Pacific marine boundary
layer background values; VIC for characterizing a continental background; and MWO for characterizing a continental, mid-
tropospheric background. At best, background conditions may only be observed intermittently from any of these sites
because each site can also be influenced by local and within-domain emissions under certain meteorological conditions. In 20
Section 4.1, we use an observation-based method to select background observations at the LJO, SCI, VIC, and MWO sites
and in Section 4.2 we compare these estimates. In Section 4.3, we discuss some air mass back trajectories and the
implications for background estimates for the LJO, SCI, VIC, and MWO sites.
4.1 Background methods
Estimating greenhouse gas enhancements at the local scale requires measurements that resolve variability in 25
background air masses (e.g. Graven et al., 2012; Turnbull et al., 2015). In the literature, several methods have been
demonstrated for identifying background observations, including applying statistical filters to look for periods with stable
measurements, filtering for meteorological conditions and/or chemical parameters, or using modelled and/or reanalysis
products in combination with observations to estimate gradients (e.g. Alden et al., 2016; Ruckstuhl et al., 2012; Thoning et
al., 1989). Methods relying on chemical filtering techniques involve monitoring multiple species to identify pollution events 30
or to inform about the sensitivity of a site to local pollution, while methods relying on meteorological filters assume some
prior knowledge about the transport of polluted air masses to the site.
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In this study, we used a data selection approach based on simple statistical filtering criteria, where steady CO2 and
CH4 mole fractions are used as an indicator of background air. Using this approach, we aim to estimate a local continental
and marine background that can be used to estimate CO2 and CH4 enhancements in Los Angeles with relatively low-latency
(i.e. with reduced delays such that near-real time atmospheric monitoring of the enhancement signal will be possible). Our
data selection approach relies on several criteria: (1) a small degree of variability within a 1 hour period, and 2) small hour-5
to-hour variability, and (3) persistence of the first two conditions for several hours. Based on these criteria, we should be
able to exclude observations that are impacted by local emissions or recirculation effects at the continuous observation sites.
This data filtering approach does not rely on the availability of any other observations (i.e. winds, boundary layer height,
etc.). In this sense, we consider this background selection algorithm to be very operational in that it can be used to estimate
background mole fractions in real time or near-real time. 10
LJO and SCI “Marine” Background and VIC “Continental” Background Estimates: The LJO, SCI, and
VIC air observations were filtered according to the same criteria. Our data filtering criteria loosely follow the preliminary
selection criteria discussed by Thoning et al. (1989) and were as follows: (1) Check for stability of the CO2 and CH4
observations within 1-hour and only retain measurements if the 1-hour SD is <0.3 ppm CO2 and <5 ppb CH4; (2) Check for
large hour-to-hour changes in CO2 concentration and retain measurements if the hour-to-hour difference is less than 0.25 15
ppm CO2 (no hour-to-hour criteria were used for CH4); (3) Retain only those observations with six or more consecutive
hours that meet criteria 1 and 2. After applying the selection criteria respective to each site, the CCGCRV curve fitting
software was used to estimate a "smooth curve" fit to the remaining observations (Thoning et al., 1989;
http://www.esrl.noaa.gov/gmd/ccgg/mbl/crvfit/crvfit.html). The curve-fitting parameters are given in Appendix A3. The full
time series, selected data and "smooth curve" results are shown in Figure 3 and the final smooth curve results are shown in 20
Figure 4 (top panels).
MWO “Continental, Mid-Troposphere” Background Estimate: Mt. Wilson (MWO) is a mountaintop
observatory overlooking the South Coast Air Basin, approximately 1670 m agl (Figure 1). At night, the PBL is shallow and
the MWO site is more likely to be influenced by air from the free-troposphere. During the daytime, the MWO CO2 and CH4
mole fractions can be influenced by emissions from the Basin either due to upslope winds or due to the rising of the PBL 25
above MWO. Calibrated continuous in situ observations from Mt Wilson were not available at the time of this study.
Instead, we used the MWO night-time flask record from NOAA/ESRL to produce a smooth curve background estimate
using a similar approach to that described above for the SCI, LJO, and VIC sites. Flask samples have been collected at
MWO approximately every 3-4 days since 2010. Only flask samples collected between 23:00 and 05:00 hours LST (local
standard time) were used in the smooth curve fit because only night-time samples are likely to be representative of 30
background conditions. The curve fitting parameters are given in Appendix A3. The final smooth curve results are shown in
Figure 4 (top panels).
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Pacific MBL Background: The Pacific MBL reference surface was developed using weekly flask air samples from
the NOAA’s Global Greenhouse Gas Reference Network (see http://www.esrl.noaa.gov/gmd/ccgg/mbl/ and Masarie and
Tans, 1995). The MBL reference surface is a data product smoothed in time and over latitude that uses NOAA
measurements from samples that are predominantly influenced by well-mixed MBL air (typically remote, marine sea level
locations with prevailing onshore winds). The Pacific MBL product provides a 2-D (latitude and time) representation of CO2 5
and CH4 mixing ratios along the Pacific boundary of North America based on the subset of GGGRN MBL sites in the
Pacific Basin. We compare the results from SCI, LJO, VIC, and MWO to the Pacific MBL reference surface in Figure 4.
We note that the method used to estimate background would fail to give a measure of influences from outside the
domain under some conditions. Below we compare the background estimates described above (Section 4.2) and discuss
some meteorological considerations for background estimation (Section 4.3). 10
4.2 Comparison of background estimates
We compared the background estimates derived from the SCI, LJO, VIC, and MWO sites during 2014-2015 with
the 2-D Pacific marine boundary layer (MBL) reference from roughly 33.4°, 36.9°, and 40.5° N (Figure 4). There are small
but systematic differences in the background curves determined for each site.
For CO2, the seasonal cycle at SCI and LJO is more similar to the Pacific MBL estimates than the MWO and VIC 15
results. The SCI and LJO background estimates show more pronounced CO2 minima in the summer relative to VIC and
MWO, similar to the MBL estimate from 33.4° N. This suggests that under the appropriate filtering criteria, the LJO and
SCI observations can be used to derive a marine background estimate for CO2. During summer months, the background
derived from VIC and MWO are differ from the MBL estimates by up to ~7 ppm CO2.
Overall, the differences CO2 background estimates from SCI, LJO, VIC, and MWO are less than ±6.5 ppm CO2 in 20
summer and ±3 ppm CO2 in winter relative to the Pacific MBL estimate from 40.5° N. During summer 2015, the marine
background estimates from LJO and SCI are slightly higher than the Pacific MBL estimate from 40.5° N, with a maximum
CO2 difference of roughly +3 and +5 ppm CO2 for LJO and SCI, respectively (Figure 4). During winter 2015, the marine
background estimates from LJO and SCI are slightly lower than the Pacific MBL estimate from 40.5° N (maximum
differences of roughly -3 ppm CO2). This is somewhat surprising given that there is more variability in the origin of the 25
incoming air masses during winter months (Figure 5).
CH4 background estimates from SCI, LJO, VIC, and MWO are less similar to one another during summer
compared to other months (Figure 4). Overall, the differences from the Pacific MBL estimate from 40.5° N range from -20
and +60 ppb CH4 during summer months and ±30 ppb CH4 during all other months. The SCI and LJO background estimates
are more similar to the Pacific MBL background during almost all times of year compared to VIC and MWO. For SCI, the 30
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differences from the Pacific MBL estimate ranging from -31 to +2 ppb CH4 during summer and from -35 to +10 ppb CH4
during the rest of the year. During summer 2015, the CH4 background derived from LJO is very different from the other
marine background estimate. A landfill near the LJO site could influence the observations at this site. This hypothesis could
be confirmed using footprint analysis. Further refinement of the data selection algorithm could also provide better agreement
between the CH4 background estimates. 5
Our results show that during most of the year, the differences in background mole fractions estimated from each of
the remote “extra domain” sites are small relative to the enhancement (discussed further in Section 5). The median
differences between the Pacific MBL estimate from 40.5° N and the other background estimates from SCI, LJO, VIC, and
MWO are: -0.8, -0.8, -0.5 and -1.3 ppm CO2 and -3.5, +1.6, -7.8, and -11.5 ppb CH4. As shown below in Sections 5 and 6,
this is ~15-17% of the median CO2 enhancement and ~10-13% of the median CH4 enhancement at the USC and FUL sites. 10
4.3 Back-trajectory analysis
Our approach for estimating background mole fractions thus far has ignored variations in atmospheric transport. In
reality, winds transport air masses in and through the LA Basin on various timescales. Therefore, the optimal background
site for selecting observations could vary diurnally, weekly, monthly, and/or seasonally. Wind back trajectories can be useful
for selecting a primary background site, based on the prevailing winds. We performed a simple back trajectory analysis and 15
below discuss some preliminary conclusions based on that analysis. Results in Figure 5 are shown for 14:00 LST (local
standard time), however, in general, the back trajectories computed for 12:00 and 16:00 LST show similar results.
We computed twenty-four hour back trajectories for winds arriving in Pasadena at 14:00 LST using NOAA’s
HYSPLIT model (Figure 5; Stein et al., 2015; Rolph, 2016). During the warmer months (spring/summer, or roughly May
through September), winds enter the Basin almost exclusively on-shore, originating over the ocean. These air masses 20
generally travel south along the coast before being directed inland. Conversely, during the cooler months (fall/winter
months, roughly November to March), there is much more variety in the provenance of the air masses (Figure 5). A
significant fraction of days have off-shore winds (i.e. from the north to northeast, and originating from the Mojave desert
region over the mountains), or could have Santa Ana-like conditions, which are a typical mode of variability for the Los
Angeles area during November to March (e.g. Conil and Hall, 2006). During offshore wind conditions, coastal sites such as 25
La Jolla or San Clemente Island may not be relevant choices for selecting background observations as these sites may be
subject to outflow and recirculation of an air mass from over land. Coastal ("Catalina") eddies are also common occurrence
along the CA bight, which is the mostly convex part of the Southern California coastline (Figures 1 and 5). Conditions that
favor coastal eddies are most common between April and September, though they develop at almost any time of the year
(Rahn and Mitchell, 2016). During such conditions, a site northwest of the Los Angeles Basin may be a more relevant choice 30
for background. However, as we showed in Section 4.3, the MBL background derived using the SCI or LJO sites was very
similar to the Pacific MBL reference surface between roughly 33-40° N.
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At least some of the differences in our background estimates from the LA sites can be explained by differences in
the prevailing meteorological conditions and a lag in the transport of air masses between the sites. The VIC and MWO sites
show larger differences from the marine background estimates during summer months for both CO2 and CH4. For VIC,
there is virtually no CO2 or CH4 data meeting the selection criteria during the summer and early fall months (Figure 3). The
back trajectory analysis showed that onshore flow conditions were more consistent from roughly May to September, during 5
the same period when our background algorithm failed to find VIC observations meeting the stability criteria (Figures 3 and
4). The VIC inlet elevation (1370 m asl, 100 m agl inlet height) is only roughly 200 m lower than MWO (1670 m asl). The
smooth curve estimate from VIC is similar to that of MWO, suggesting these two sites may be sensitive to similar air
masses. Therefore, we conclude that the VIC and MWO sites may not be relevant choices for background during summer,
when onshore flow patterns dominate. 10
Our back trajectory analysis does not have the temporal resolution necessary to evaluate diurnal land-sea breezes.
The spatial resolution of the NAM12 meteorological data used by HYSPLIT is 12 km. From this analysis, we can certainly
see seasonal variations of the wind direction and the incoming air masses for the LA basin. We do not compare the
day/night differences in meteorology, such as land/sea breezes, in our analysis, though we note that these circulation patterns
could be important for understanding the greenhouse gas variability (especially at coastal sites such as SCI, LJO, and 15
possibly IRV). Such analysis would require a higher resolution model, such as the 1.3 km resolution WRF-Chem model
discussed by Feng et al. (2016), which is beyond the scope of this study. Feng et al. (2016) found that sea breeze prevailed
over the LA megacity at ~14:00 LST during the May/June 2010 (CalNex) study. Furthermore, the modelled topography of
the Palos Verdes Peninsula was found to divide the sea breeze into west and southwest onshore flows that later converged in
the Central Basin. In general, transport models do not do well overnight ((Feng et al., 2016), which makes evaluation of 20
diurnal variations challenging using modelled CO2 or CH4 output. Future modelling studies that overlap with the CO2 and
CH4 records will be needed to evaluate the impact of land/sea-breezes on CO2 and CH4 observations from coastal sites and
could also improve our understanding of the impacts winds induced by topography on the greenhouse gas observations.
Feng et al. (2016) used results from a forward model simulation to explore correlations in CO2 concentrations in a
model framework. They showed that CO2 is trapped and accumulates due to the mountain barrier, leading to CO2 25
enhancements at in-basin sites relative to the desert site at VIC. Feng et al. also found that while the modelled CO2 levels at
the VIC desert site were mainly anti-correlated with the LA Basin sites, CO2 that accumulated in the Basin could
occasionally be pushed over the mountains and into the desert due to episodic strong sea breezes and onshore flow
conditions. This supports our conclusions that VIC and MWO (night-time) observations may not always provide
representative background mole fractions, particularly during summer months when onshore flow conditions prevail. It is 30
important to note that our approach for evaluating background mole fractions from MWO relied on night-time flask
observations only, which were collected between 23:00 and 05:00 hours LST. Feng et al. refer to MWO as “western basin”
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site, exhibiting spatial CO2 correlations similar to the GRA, CIT, USC, and COM sites. Feng et al. (2016), but do not discuss
day/night differences in the sensitivity of the MWO site. At night, we expect the PBL to be shallower, reducing the
likelihood that air from the SCB will be transported to the MWO site. In future work, we plan to analyze continuous
observations in conjunction with the night-time flask record from MWO to evaluate the diurnal variability in CO2 and CH4
observations at this site. While the simulations discussed by Feng et al., (2016) only cover a brief period during 5
spring/summer 2010, future modelling studies over longer periods (e.g. one year) could improve our understanding of
variations in the mesoscale circulation in the LA megacity and the impacts on the observed CO2 and CH4 mole fractions.
The variety and complexity of meteorology in the South Coast Air Basin suggests that a more sophisticated background
selection algorithm is needed to determine the site that is “upwind” during different prevailing wind conditions. Future
model analyses could also help determine when our observation sites are most relevant for estimating background. 10
Overall, the LJO and SCI background estimates establish a marine sector background to within roughly 1 ppm CO2
and 10 ppb CH4 (excluding the period during summer 2015 discussed above). SCI is the most representative of local marine
background conditions for both CO2 and CH4 throughout the year. Therefore, we use SCI as the background reference site
to calculate CO2 and CH4 enhancements for the LA surface sites (see below).
5 CO2 and CH4 enhancements 15
We calculated the average enhancement at each site using the SCI marine background reference. Moderate to large
CO2 and CH4 enhancements (ΔCO2 and ΔCH4) are observed above the background mole fractions. Tables 4 and 5 show
statistics regarding the enhancement at each site estimated for all hours and midday hours (12:00-16:00 LT, not including
adjustment for daylight savings time) during 2015. Figure 6 shows the ΔCO2 and ΔCH4 values at 9 sites for all hours and
midday hours, with sites arranged by latitude. We do not discuss the results from the Ontario site (ONT) in detail because 20
measurements were only available from Sept-Dec 2015 and therefore are not representative of the annual average.
The median enhancement during all hours was 21.4, 18.8, 16.3, 15.1, 10.7 ppm ΔCO2 and 121.0, 148.0, 106.1,
100.6, and 74.1 ppb CH4 during 2015 at the USC, FUL, COM, GRA and IRV sites, respectively. During midday hours, the
period that is most relevant for flux inversions, the median enhancement was 13.8, 12.2 10.1, 10.4, 5.8 ppm ΔCO2 for the
USC, FUL, COM, GRA and IRV sites, respectively (Figure 6 and Table 4). 25
The median CH4 enhancement was 148, 106, 101, 121, and 75 ppb ΔCH4 for the USC, FUL, COM, GRA and IRV
sites, respectively. During midday hours, the median enhancement during 2015 was 81.4, 58.6, 52, 70.4, and 40.2 ppb ΔCH4
at the USC, FUL, COM, GRA and IRV sites, respectively (Figure 6 and Table 5).
Overall, the results suggest that the CO2 and CH4 enhancements are characterized by a large degree of spatial and
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temporal variability (Figures 2 and 6). In general, the enhancements of both gases are more pronounced in winter relative to
spring and summer months (Figure 2). Prior studies have shown that anthropogenic (fossil) CO2 sources dominate in winter
months due to increased emissions from the residential and electric production sectors. On average, more urbanized areas
such as the USC site near Downtown LA exhibit larger median ΔCO2 and ΔCH4 values during 2015 (Figure 6 and Tables 4
and 5). CH4 shows a slightly different spatial distribution in the median enhancement relative to CO2, with the second 5
largest CH4 enhancements observed at the GRA site, which is a suburban site located in the San Fernando Valley.
The CO2 and CH4 enhancements also exhibit long-tail distributions, a reason we report the median and interquartile
range in Tables 4 and 5 in addition to the other statistics. As mentioned earlier, relatively large CH4 excursions, on the order
of 4 ppm above background or more, are observed throughout the GRA time series (Figure 2). The GRA site also exhibits a
long-tail distribution with respect to the CH4 enhancements, which is more pronounced compared to the other sites, even 10
during midday hours (see Supplemental materials Figure S6, which shows the outliers in addition to the median and
interquartile range). Many of the larger enhancements occur during night-time/early morning hours. The smaller
enhancements during midday hours relative to night suggest that GRA may be sensitive to a local CH4 source at night, when
the PBL becomes shallower and could be more stratified (Figures 2 and 6 and Tables 2–5). The long-tail distribution for
CH4 in Los Angeles and the prevalence of fugitive CH4 emissions across the LA urban landscape was previously 15
demonstrated by Hopkins et al. (2016), using extensive mobile surveys. Hopkins et al. (2016) identified 75% of methane
hotspots to be of fossil origin, while 20% were biogenic, and of 5% of indeterminate source using the ratio of ethane to
methane (C2H6/CH4). They also found that fossil fuel sources accounted for 58-65% of methane emissions and suggested
that there are widely distributed methane sources, primarily of fossil origin, that are not included in bottom-up inventories.
In future work, detailed analysis of winds, measurement footprints, and tracer/tracer analyses will be used to evaluate the 20
origin of the anomalous CH4 enhancements.
6 Uncertainty in the CO2 and CH4 enhancements (UEnhancement)
Both analytical uncertainty and imperfect knowledge of the composition of background air limit the precision of
observation-based estimates of local- or regional-scale greenhouse gas enhancements (e.g. Graven et al., 2009; 2012a;
2012b; Turnbull et al., 2009; 2015). We estimate the uncertainty in the enhancement as follows: 25
(UEnhancement)2 = (Uair)2 + (UBG)2 (4)
where UEnhancement is the total uncertainty in the enhancement of CO2 or CH4 and is proportional to the quadrature sum of the
uncertainty in the air measurement (Uair) and the uncertainty in the background mole fraction (UBG). We note that UBG is not
statistically independent of Uair because UBG is derived from measured values. In the remainder of this study, we explore the
analytical uncertainty in our measurement approach and calibration strategy (Uair) using data from the LJO site (Section 6.1) 30
and the uncertainty in the background mole fraction using the marine reference background from SCI (Section 6.2).
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6.1 Measurement uncertainty analysis (Uair)
We model the analytical uncertainty in the air measurements following the general methods outlined in Andrews et
al. (2014), using the quadrature sum of multiple uncertainty components:
(Uair)2 = (uextrap)2+ (uh2o)2 + (uM)2 (5)
where 5
uM = uTGT (6)
or
(uM)2 = (up)2 + (ub)2 +(uscale)2 (7)
(whichever is greater).
Equation 5 describes Uair, the total uncertainty in the reported air mole fractions, and its individual components, 10
which have units in mole fraction CO2 or CH4 (ppm or ppb). In Eq. 5, uextrap is the extrapolation uncertainty, or the
uncertainty introduced because the measured mole fraction of the air sample differs from the value of the calibration
standard (Section 6.1.1), and uh2o is uncertainty from the treatment of water vapor (Section 6.1.2). In Eqs. 6-7, uM is the
greater of two terms, defined by either uTGT the uncertainty determined by the target tank measurements or the quadrature
sum of several terms: up, the analyzer precision (Section 6.1.4), ub, the analyzer calibration baseline uncertainty (6.1.5), and 15
uscale the scale reproducibility (Section 6.1.6). In Eq. 6, uTGT is equivalent to a Root Mean Square Error (RMSE), and is
estimated using the corrected target tank residual over 10 days, similar to Andrews et al. (Section 6.1.3).
Overall, Eqs. 5 to 7 describe a generic algorithm that can be applied to other analyzers, as well as for CO
measurements. Time-dependent monitoring of ub, up and uTGT is useful when tracking analyzer performance. Although the
overall measurement uncertainty is typically small, an increase in any of these values (ub, up and uTGT) may indicate problems 20
with a specific analyzer. Thus, this system could be used to generate alerts for the data user to identify periods when an
analyzer is performing poorly or to indicate periods when the measurements may not be useful for atmospheric inverse
modelling studies.
6.1.1 Extrapolation uncertainty (uextrap)
We corrected the air measurements in Figure 2 using a one-point calibration method. As a result, any air 25
measurement that is different from the value of the calibration standard is subject to an extrapolation uncertainty, uextrap,
which is the uncertainty introduced because the measured mole fraction of the air sample differs from (and in many cases is
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larger than) the value of the calibration standard (around 400 ppm CO2 and 1850 ppb CH4). We estimate uextrap as follows:
uextrap = |ε| × |Xcorr Xassigncal| (8)
where ε (described below) has units of ppm/ppm or ppb/ppb and is multiplied by the absolute value of the difference
between the sampled air concentration and the and assigned calibration tank value (|Xcorr Xassigncal|).
Our approach relies on independent estimates of ε, the error due to the single-point calibration method, to determine 5
the magnitude of the systematic and random components of the error in our calibration method. Ideally, initial estimates of ε
would be determined empirically via testing each analyzer in a laboratory prior to deployment in the field to provide
estimates of the magnitude of the extrapolation uncertainty (e.g. Andrews et al., 2014; Richardson et al., 2012). At the time
of this study, it was not possible to test many of the CRDS analyzers in a laboratory prior to deployment in the field because
high mole fraction standards spanning the range of CO2 and CH4 measurements expected in LA were not available. 10
Since a suite of calibration standards was not available at the time of this study, we determined ε using the average
"correction" slope determined from analysis of a series of standard tanks at different mole fraction tanks on a suite of CRDS
analyzers. Within the LA network, only the LJO and VIC analyzers had field calibration data from high mole fraction tanks
available at the time of this study. We used the limited measurements of these high mole fraction tanks (approximately 500
ppm CO2 and 2600 ppb CH4) to compute an average ε over the period when a high mole fraction tank was available. We also 15
investigated laboratory calibration data from the seven additional Picarro CRDS model G2401 and G2401-m analyzers, as
described below. These analyzers are not part of the network, but are similar to the CRDS analyzers used in the field in the
LA network.
Calibration analyses for the seven independent analyzers were performed at NOAA/ESRL during 2014 to 2015 with
between 3 and 7 reference tanks calibrated on the WMO scales for each gas (up to approximately 470 ppm CO2 and 3060 20
ppb CH4). A single standard tank (the tank with a CO2 value closest to 400 ppm) was set as the calibration standard
(Xassigncal) and was used to correct the CRDS reading for the other standard gases using Eq. 2. Next, we plotted the residual
of the corrected mole fraction for each tank measurement and its assigned value (Xcorr Xassign) as a function of the
difference in the assigned mole fraction between a given tank and the calibration tank (Xassignspan Xassigncal). The slope
of this relationship is equivalent to ε for a given analyzer. Estimates of the correction factor, ε, and regression statistics for 25
these seven analyzers are summarized in Tables 6 and 7 (the data are shown in the Supplemental materials, Figures S1 and
S2).
The values of the slope correction (ε) are 0.0027 and 0.0018 ppm/ppm for CO2 and 0.0012 and 0.0060 ppb/ppb for
CH4, for the LJO and VIC analyzers respectively. These results are compared with the other analyzers in Table 6. For CH4,
all analyzers show a clear linear relationship between the error and the mole fraction of the tank, and there is very little 30
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difference in the slope between different analyzer units (see Supplementary materials, Figure S2). Interestingly, for CO2, we
find that the two older analyzers (CFKBDS-2007 and -2008) have larger slopes, while the majority of the analyzers have
very little dependence on the mole fraction and have errors close to zero (see Figure S1). The results in Table 6 are used to
estimate the magnitude of the error in the corrected air sample mole fractions caused by assuming a constant analyzer
sensitivity, or slope correction. The average value of ε from all 9 analyzers was used to estimate an extrapolation to our 5
single-point calibration and the uncertainty in this correction (uextrap). The slope from these calibration experiments (ε) gives
an estimate of the error in the single point calibration and how it increases when the measurement is farther from the value of
the single calibration point. Overall, uextrap is proportional to the fractional difference between the mole fraction of the air
sample and that of the ambient-level calibration tank. The average and standard deviation of ε also provide estimates of the
systematic and random components of the error in the single-point calibration method (Table 7). 10
We also estimated the error associated with the single-point calibration strategy using Eq. 8 and various estimates of
ε for 3 cases: (1) the average and standard deviation of ε from all 9 analyzers, (2) the average ε from 7 analyzers (excluding
LJO and VIC), and (3) an instrument specific estimate of ε from the LJO site (Table 5). Next, we estimated the error
assuming an hourly average air measurement of 500 ppm CO2 and 6000 ppb CH4 (i.e. roughly 100 ppm CO2 and 4000 ppb
CH4 enhancement above the "near ambient" calibration standard). Finally, we corrected air data from the LJO and VIC sites 15
using an "Alternate Calibration Method," during times when a limited number of measurements of a high mole-fraction CO2
and/or CH4 standard were available for analysis (see Appendix, Figures A2 and A3). Overall, the difference between the
single-point (default) calibration method and the "Alternate Calibration Method" are <0.2 ppm CO2 and <5 ppb CH4 for the
majority of air measurements. We also estimated the maximum correction using both approaches (the "Alternate Calibration
Method" and a correction and error based on uextrap), and the results are summarized in Table 6. 20
While the initial results are very promising, and the corrections tend to be small, there is a large degree of
variability in the estimates of ε for individual analyzers. The value of ε can be different for different analyzers and can also
change over time for a single analyzer (Tables 6 and 7 and Figures S1 and S2). Based on the experiments discussed here, our
current calibration strategy could be modified to correct the concentration data using the mean value of ε found from all the
analyzers and estimating an uncertainty in that correction. However, our approach for estimating ε is based on relatively 25
small statistical sample of analyzers. Furthermore, the two estimates we do have from the LJO and VIC field sites only rely
on one additional calibration point other than the calibration tank, making it difficult to estimate a robust fit for these
analyzers. An estimate of ε for each analyzer in the field (or from a larger statistical sample of analyzers) is needed to
provide a robust estimate of the mean ε to correct the air sample data. Values of ε could also be estimated for the analyzers
deployed in the field, for example, by deploying a suite of calibration standards with varying concentrations of CO2 and CH4 30
(e.g. a round-robin). We have chosen not to correct the data and keep it tied to the single-point calibration until more
experimental evidence can be obtained. In the future, the surface network will move to a 2-point calibration strategy. This
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will rely on the availability of high-mole fraction tanks for deployment in the field, and a calibration uncertainty that is lower
uncertainty than our current estimates for uextrap.
6.1.2 Uncertainty associated with water vapor (uh2o)
The presence of water vapor in the sample air contributes to the uncertainty in the CRDS measurements. Below we
describe three potential sources of uncertainty in the measurements due to water vapor: 1) the coefficients used to determine 5
the water vapor correction, which can vary from instrument to instrument, 2) bias due to imperfect drying, and 3) random
noise in the H2O measurement reported by the CRDS analyzer, which ultimately gets incorporated in the water vapor
correction (Rella et al., 2013).
The Picarro CRDS analyzers use a factory default water vapor correction model that relies on the parameters
derived by Chen et al. (2010):
10
!"!!"#
!"!!"#
=1+𝑎𝐻!"# +𝑏𝐻!"#
! (9)
!"!!"#
!"!!"#
=1+𝑐𝐻!"# +𝑑𝐻!"#
! (10)
where Hrep is the water vapor mixing ratio reported by the analyzer, (CO2)wet and (CH4)wet are the uncorrected CRDS, wet-gas
mole fractions reported by the analyzer, (CO2)dry and (CH4)dry are the dry-gas mole fractions, while a, b, c, and d are
experimentally determined parameters (where a = -0.012000, b = -0.0002674, c = -0.00982, and d = -0.000239). This 15
correction is currently being applied to the analyzers in the LA network. Users are free to design and perform their own
experiments and derive parameters specific to each instrument (Nara et al., 2012; Rella et al., 2013; Welp et al., 2013).
However, while an instrument specific correction of water vapor could potentially lead to reduced uncertainty, prior
laboratory studies have also found that the benefits of an instrument specific correction are small at low water vapor levels
(Nara et al., 2012; Rella et al., 2013). 20
The Nafion drying system described in Section 2.3 and by Welp et al. (2013) allows us to stabilize the water vapor
concentrations in the sample gas stream (Hrep in Eqs. 9-10) to 0.1±0.01%. With this drying system, the uncertainty in the
water vapor correction drops to 0.015 ppm for CO2 and 0.21 ppb for CH4 when using the factory parameters described above
(Rella et al., 2013; Welp et al., 2013).
The use of a Nafion dryer could also potentially introduce a bias due to imperfect drying. A slight permeation of 25
CO2 and CH4 can occur across the membrane, especially when the Nafion membrane is wet (e.g. Ma and Skou, 2007; Welp
et al., 2013). In our measurement setup, running the dry standard gases through the Nafion dryer significantly reduces this
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bias effect. The water vapor concentration from the dry standard gas runs is similar to that of the preceding air
measurements. We find that the water vapor mole fraction in the air measurements after a standard is run drops by 0.01%
(from 0.10% to 0.09%). A similar effect has been described by Rella et al. (2013). We estimate the Nafion bias in our
system based on this 0.01% variability in water vapor to be -0.011 ppm for CO2 and 0.00028 ppb for CH4 based on
laboratory experiments performed at the SIO laboratories with the same Nafion drying system used in the field. Details about 5
the laboratory experiments are available in the Supplementary materials (see Figure S3).
A final source of uncertainty regarding water vapor correction comes from the variability of the water vapor
measurement on the CRDS analyzers. We estimate this to be 0.014 ppm for CO2 and 0.069 ppb for CH4 at the water vapor
concentrations of our measurements (Rella et al., 2013; Welp et al., 2013).
The total uncertainty due to water vapor (uh2o) is the quadrature sum of the water vapor correction uncertainty, the 10
Nafion-induced bias due to changes in water vapor, and the variability (noise) of the water vapor measurements. Therefore,
we estimate uh2o is 0.0233 ppm for CO2 and 0.221 ppb for CH4 across the network and it is assumed to be constant at all
times.
6.1.3 Uncertainty derived from target tank measurements (uTGT)
We define uTGT in Eq. 6, where the target tank is treated as an unknown and the measured value is compared to the 15
tank assignment to calculate the root mean square error (RMSE):
𝑢!"! =𝑋𝑐𝑜𝑟𝑟!"! 𝑋𝑎𝑠𝑠𝚤𝑔𝑛!"!
! (11)
where, 𝑋𝑐𝑜𝑟𝑟!"! is the corrected target tank measurements and XassignTGT is the assigned value of the target tank by the
calibration laboratory (NOAA/ESRL or SIO). The assigned values are constant over the lifetime of the cylinder and are
determined based on laboratory measurements traceable to the WMO scales. Errors in the tank assignments are typically 20
small and would result in a bias in the measurement, rather than a random error (see Section 6.1.6). To calculate 𝑋𝑐𝑜𝑟𝑟!"!,
the uncorrected CRDS target tank concentration readings are treated as an unknown sample and are corrected using Eq. 2.
For each target tank measurement, uTGT is calculated as the RMSE (Eq. 11) over 11 target measurements centered on the
measurement time (this is usually a 10-day period). Then, this time-dependent uTGT is interpolated in time onto all the air
measurements. Overall, uTGT is equivalent to a RMSE and includes errors in the assigned value of the calibration tank and 25
the target tank, and also encompasses other errors (e.g. the instrument precision and the calibration standard baseline
uncertainty), as well as additional and possibly unknown errors due to delivery of air to the analyzer downstream of the
Valco valve. Drift in either the calibration or target cylinders will also manifest as an increasing uTGT. In this way, uTGT is
useful as a diagnostic of instrument performance.
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6.1.4 Analyzer precision (up)
The analyzer precision (up) is defined as the standard deviation of the 10-minute daily calibration standard tank
measurement:
up = σcal (12)
where σcal is the standard deviation of the uncorrected CRDS, dry mole fraction measurements for the calibration tank at 5
roughly 2.5-second resolution. Our definition of up is different from that described by Andrews et al., (2014), where the
analyzer precision was defined as the standard error of the calibration measurements. To use the standard error, we must
assume statistical independence of the measurements and estimate a maximum value for N, the number of samples in the
average that reduce the uncertainty.
We performed an Allan deviation analysis to estimate stability of the Picarro CRDS analyzer due to noise 10
processes. The Allan deviation is the square root of the Allan variance (Allan, 1966, 1987) and was plotted as a function of
averaging time for calibration runs at the LJO site during January 2016 (Figure S4). During this month, the calibration tank
was run 28 times through the CRDS analyzer for 30 minutes at each time (10 minutes longer than the normal calibration run
period, for quality check purposes). We omitted the first 10 minutes of data and performed the Allan deviation analysis on
the next 20 minutes of data for each of the 28 calibration runs. We found that the instrument variability does not average 15
with a slope of -1/2 as would be expected for a white noise profile, indicating correlation in the noise at various longer time
scales. The deviation (noise) therefore does not decrease as the inverse square root of the averaging time ( 𝑁), as it would
for white noise. Filges et al. (2015) found a comparable result using similar CRDS units. Figure S4 shows the Allan
deviation analysis for a subset of six (for figure clarity) of these calibration runs over the course of the month, also indicating
that the characteristics of the noise in the analyzer varies. The deviation does decrease with averaging time, but not in a 20
consistent manner. Therefore, we have chosen not to compute the standard error in the mean by dividing the standard
deviation by the square root of the number of measurements, because the characteristics of the noise in the analyzer vary
with time and the data does not fit the criterion of the measurements being truly independent. We therefore quantify the
precision of the analyzers as the 2.5-second standard deviation independent of averaging time, recognizing that it is likely an
overestimate of the analyzer precision. This uncertainty for CO2 and CH4 is small compared to other sources, so we chose to 25
retain it, considering that in the future (or for other species, such as CO), we will model the precision in a more robust
manner.
6.1.5 Calibration baseline uncertainty (ub)
To estimate the calibration baseline uncertainty (ub) we follow a process similar to that described by Andrews et al.
(2014). First, we calculate three different possible time series of the calibration tank measurement (X’) to estimate Scal (the 30
instrument sensitivity measured for the calibration tank). The first is an interpolation onto air data using every calibration run
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(Scal). The second and third time series use alternate sampling of the calibration tank time series (i.e. by either odd or even
sampling of every other daily calibration run) to interpolate X’ onto the time series of the air sample data (see Figure S5).
Next, we calculate the dry air mole fraction corrected at each point using each of these three different time series. The
maximum uncertainty, ubmax, is estimated as the standard deviation of the three corrected mole fractions (black solid line,
Figure S5). The actual uncertainty, ub, is equal to this maximum value (ubmax) at the halfway point in time between 5
subsequent calibration runs, and goes to zero at the time of a calibration run, since that that time the calibration value is
known exactly. Thus, ub is equal to ubmax weighted by the time difference between an air sample measurement and the
adjacent calibration run (dashed line, Figure S5).
6.1.6 Uncertainty in calibration tank assignments
Absolute scale accuracy includes uncertainties in the values assigned to the primary calibration standards, as well as 10
scale propagation errors (Andrews et al., 2014). Here we report an expanded uncertainty (95% C.L., approximately 2σ): 0.20
ppm at 400 ppm CO2 (WMO X2007 scale) and 3.5 ppb at 1850 ppb CH4 (WMO X2004A scale), where the total uncertainty
is a relatively small function of the measured mole fraction. However, in our case, all measurements are calibrated relative
to the same (WMO) scale, so scale reproducibility is the relevant metric for assessing measurement compatibility over time
and between sites. Similar to Andrews et al. (2014), the reported scale reproducibility is 0.06 ppm for CO2, and 1.0 ppb for 15
CH4 (2σ) (B. Hall, personal communication). We use the 1σ scale reproducibility (uscale) in the calculation of Uair (0.03 ppm
CO2, and 0.31 ppb CH4)
Cylinder drift has not been discussed and could also impact this component of the measurement uncertainty.
Andrews et al. (2014) report a mean difference between pre- and post-deployment tank calibrations of CO2 and CH4. CO2
has rarely been observed to drift in cylinders, while CH4 standards are very stable. Andrews et al. (2014) report a mean 20
difference between pre- and post-deployment tank calibrations of 0.02±0.05 ppm CO2 (post- minus pre-deployment from
177 tanks analyzed over approximately 10 years). CH4 standards are generally very stable and field calibration residuals
reported for CH4 had not indicated any drift in the tanks (for CH4 absolute stability is reported as 0±0.1 ppb yr-1
(Dlugokencky, 2005; Dlugokencky et al., 1994). CH4 standards were generally stable, (Andrews et al., 2014; Dlugokencky,
2005). At the time of this study, none of our field calibration cylinders for the LA surface network had final calibrations; 25
however routine field measurements of standard tanks to date do not indicate significant drift in either gas.
6.2 Uncertainty due to background
We used the standard deviation of the fit residuals to define an uncertainty in the background mole fraction as
follows:
(UBG)2 = (XRMSE)2 (13) 30
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where XRMSE is the standard deviation of the fitted curve residuals. For the SCI reference curve fit, UBG is 1.1 ppm CO2 and
11.7 ppb CH4.
6.3 Comparison of uncertainty estimates
Figure 7 shows the time-dependent analytical uncertainty estimates for the LJO site during 2015 and Table 7 gives
the average values for each term. We assigned fixed values for uscale (0.03 ppm CO2 and 0.31 ppb CH4) and uh2o (0.0233 ppm 5
CO2, 0.221 ppb CH4). Overall, uh2o, and uscale are small components of Uair, the overall measurement uncertainty. We do not
have time dependent estimates of all the uncertainty terms used in calculating Uair for every analyzer.
Under normal operating conditions, the calibration baseline uncertainty (ub) and the analyzer precision (up), are also
negligible. The average ub is 0.0042 ppm and 0.054 ppb for CO2 and CH4 respectively, with no significant outliers (based on
the average for 11 analyzers deployed in the field). Similarly, up is a very small component of the overall uncertainty. 10
Similarly, the values for analyzer precision across the network are similar to those derived from the LJO analyzer under
normal operating conditions (roughly 0.024 ppm CO2, 0.22 ppb CH4 for the 20-minute average air observations, and 0.011
ppm CO2 and 0.12 ppb CH4 for the 1-minute average air observations). Both ub and up can become non-negligible
components of the uncertainty if there are problems with either the CRDS analyzer, or the delivery of calibration gas to the
analyzer. For example, the standard deviation of some calibration runs may be higher than the values reported for the LJO 15
analyzer suggest, either because of analyzer noise increasing due to hardware or software problems, analyzer drift during a
calibration run, or because a limited number of calibration measurements were available to calculate an average due to
analyzer problems. Therefore, the values derived from the LJO analysis represent the minimum quantities we expect for up,
which is representative of the precision from a well-performing analyzer.
Overall, uextrap, provides an estimate of the uncertainty due to the single-point calibration method, which is the 20
largest component of uncertainty in the air measurements (Figure 7 and Table 7). We find that uextrap is linearly dependent on
the difference between the mole fraction of the air sample and that of the ambient-level calibration tank, at least over the
range of mole fractions tested (see Supplementary materials, Figures S1 and S2). As described earlier, we do not have
instrument-specific estimates of ε for every analyzer to use in estimating uextrap. Therefore, we assumed constant values for ε
based on the average of the 9 analyzers shown in Table 6. During 2015, the average uextrap value estimated for the LJO 25
analyzer is 0.047 ppm CO2 and 0.46 ppb CH4. The magnitude of uextrap is larger for air data with higher mole fractions, and
scales as a percentage of the difference in the mole fraction of the air sample above the assigned value of the calibration
tank. On average, the uncertainty due to uextrap results in an uncertainty in the enhancement on the order of 0.0025 ppm/ppm
(0.25%, or 0.25 ppm for a 100 ppm enhancement) for CO2 and 0.003 ppb/ppb (0.3% or 0.30 ppb for a 100 ppb enhancement)
for CH4. Based on analysis of the LJO data during 2015, the average value of Uair is 0.070 ppm CO2 and 0.72 ppb CH4 30
(Table 8). Overall, these experiments show that the single-point calibration introduces rather small errors in the final mole
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29
fraction assignments for CO2 or CH4, and especially relative to the enhancement above background (Figure 7 and Tables 4–
8).
We used Eq. 4 to estimate the uncertainty in the enhancement signal using the estimates of Uair and UBG for the LJO
analyzer and the SCI background estimate, respectively. Since Uair is time varying, the uncertainty in the enhancement is
also time-dependent. On average, uncertainty in the enhancement is roughly 1.1 ppm and 11.7 ppb, for CO2 and CH4, 5
respectively for the LJO air data. Overall, the uncertainty due to the assumptions about the background condition is the
largest component of the error in the enhancement. However, on an annual average basis, the total uncertainty is generally
less than roughly 5 and 15% of the enhancement in downtown LA for CO2 and CH4, respectively.
7 Summary and Conclusions
Concerns about rising greenhouse gas levels have motivated many nations to begin monitoring or mitigating 10
emissions, motivating the need for robust, consistent, traceable greenhouse gas observation methods in complex urban
domains. Observations from organized urban greenhouse gas monitoring networks such as the LA surface network are
emerging elsewhere (e.g. Shusterman et al., 2016; Turnbull et al., 2015; Xueref-Remy et al., 2016). To date, most of these
research efforts have been largely disconnected. More information flow between existing urban observational networks and
the science and applications communities is needed to understand greenhouse gas emissions from cities. Data and methods 15
for greenhouse gas monitoring in urban regions should be fully disclosed and documented with a small degree of latency to
make the best use of these atmospheric data for emissions verification and/or for informing policies more generally.
In this study, we describe the instrumentation and calibration methods used for the Los Angeles Megacity surface
network. The measurement and sample module system described here provide robust, near-continuous and unattended
measurement of CO2 and CH4 at urban and suburban monitoring stations in the South Coast Air Basin. A total of eleven 20
analyzers have been deployed thus far, and most have been operational for more than 1.5 yrs. We reported the sampling
configuration, algorithms to compute calibrated CO2 and CH4 mole fractions, and methods for estimating the local
enhancement above background and uncertainties.
We presented an observation-based method for estimating background mole fractions using measurements from
four remote, “extra-domain” sites. Our approach to background determination is useful for exploring variability in the 25
enhancement signals. Relative to the enhancements observed at most sites, there is near equivalence of continental and
marine boundary layer background conditions, except during summer months, when continental sites may not be relevant for
estimating background due to prevailing on-shore flow conditions in the basin. One strength of our observation-based
strategy for background determination is the relatively short latency with which background observations can be evaluated
(hours to days). This will be important as greenhouse gas research networks such as the LA network transition from 30
research networks into monitoring networks and will allow near real-time estimation of local greenhouse gas enhancements.
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30
The stability criteria discussed here could also be used to identify periods that are optimal for flux inversion. For example, it
may not be useful to select background observations when influences from outside the domain cause large gradients or
fluctuations within the domain. Similarly, periods that are impacted by recirculation effects are not ideal for identifying
background and thus are also not useful for estimating fluxes, and the measurement stability criteria may also be useful for
identifying such periods. 5
We calculated CO2 and CH4 enhancements in the LA megacity from during 2015 using a marine background
estimate. An urban site near Downtown LA has a median enhancement of roughly 20 ppm CO2 and 150 ppb CH4 during all
hours, and roughly 15 ppm CO2 and 80 ppb CH4 during midday hours (roughly 12-16:00 LT, local time), which is the typical
period of focus for flux inversions. “Suburban” sites show moderate, but slightly smaller enhancements, with median values
of roughly and roughly 5-10 ppm CO2 and 30-70 ppb CH4 during midday hours. Overall, the largest CO2 and CH4 10
enhancements were observed at the USC site near Downtown Los Angeles.
We also described the components of the analytical uncertainty that we believe to be most important for urban
studies. The uncertainty in the enhancement was estimated using both the uncertainty in the air sample data collected form
the measurement system and the uncertainty in the background mole fraction. The algorithm discussed here can also help
determine periods when uncertainties in the observation are small and are therefore most useful for atmospheric inversion 15
studies. The acceptable threshold for the measurement uncertainty in part depends on the question of interest, and how large
the signal is relative to a local background (i.e. the enhancement).
Our analysis shows that the uncertainty in the single-point calibration method (uextrap) is the largest component of
the measurement uncertainty. Overall, uextrap, the uncertainty in the single-point calibration strategy, scales as a function of
the enhancement in the air data (roughly 0.3% of the enhancement for both CO2 and CH4). Based on our error analysis, 20
uextrap depends on the response or sensitivity of the analyzer, which is time varying. Our assessment of uextrap could be further
improved with more estimates of the correction factor (ε) from a larger statistical sample of analyzers. Currently, our ability
to fully evaluate the magnitude of the correction to the air data is limited by the availability of high concentration standards
in the field. In the near future, the LA measurement network will begin using analyzer specific estimates of the correction
factor based on periodic measurements with high mole fraction tanks, which will allow correction of the random and 25
systematic components of the uncertainty associated with the single-point calibration strategy.
While measurement uncertainty is important for estimating gradients between sites, accurate background
determination and uncertainties in atmospheric transport will likely be more important for estimating urban enhancements
and using observations in flux inversions. Overall, the uncertainty associated with background is larger than the analytical
uncertainty; however both the analytical and background uncertainty are likely to be smaller than the uncertainty due to 30
atmospheric transport, a topic that we have only discussed briefly to provide context for the observations presented in this
study. Our results suggest that reducing the uncertainty to less than 5% of the enhancement will require detailed assessment
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31
of the impact of meteorology on background conditions over a range of conditions (e.g. following Feng et al., 2016). Future
modelling efforts for the LA Megacity Carbon Project may require equivalent attention to meteorological validation, as has
been demonstrated here for the greenhouse gas observations, due to uncertainties in atmospheric transport.
“Top down” flux inversions relying on in situ greenhouse gas observations require accurate determination of urban
enhancements relative to a local background. We calculated an expected atmospheric signal of Los Angeles carbon 5
emissions assuming emissions are distributed evenly over the roughly 17,100 km2 are of the South Coast Air Basin (SCB),
an average wind speed of 2 m/s (based on annual average wind speed observed at the USC observation site) equivalent to a
transit time of ~18 h), an average mixed layer depth of 1 km (Rahn and Mitchell, 2016; Ware et al., 2016) and estimated
emissions, (Pacala et al., 2011). Estimated annual emissions of 144 Tg CO2 y-1 would raise CO2 mole fractions by roughly
10 ppm (based on Hestia-LA 2012, see e.g. Gurney et al., 2012, 2015). Assuming an annual emissions estimate of 0.4 Tg 10
CH4 y-1 in the SCB based on a top-down study, CH4 mole fractions would be enhanced by roughly 75 ppb (Wong et al.,
2015). These estimates are consistent with the midday enhancements observed over downtown LA during 2015 (Figure 6
and Tables 4–5), and those reported previously (Newman et al., 2013, 2016; Wong et al., 2015).
In the future, urban greenhouse gas monitoring networks such as the LA surface network could also be used to
understand episodic sources or disturbance events such as fires, gas leaks, etc., which are difficult to capture with bottom-up 15
approaches. This will also require background estimation in near real-time. Co-monitoring of tracers (e.g. CO2 and CO
enhancements, calibrated with 14C measurements) is also planned as part of future work and will allow continuous or near-
continuous estimation of fossil carbon signals in Los Angeles (Miller et al., 2015). Establishing greenhouse gas
enhancements and emissions trends over a period of several years could help assist in determining the effectiveness of local
control measures and mitigation strategies. As part of future work, we plan to use forward and inverse modelling studies and 20
tracer-tracer analyses in conjunction with the calibrated CO2 and CH4 observations from the LA surface network presented
here to estimate greenhouse gas emissions fluxes, determine spatial and temporal emissions trends, and to attribute those
fluxes to specific sectors and/or sources.
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References
Alden, C. B., Miller, J. B., Gatti, L. V, Gloor, M. M., Guan, K., Michalak, A. M., van der Laan-Luijkx, I. T., Touma, D.,
Andrews, A., Basso, L. S., Correia, C. S. C., Domingues, L. G., Joiner, J., Krol, M. C., Lyapustin, A. I., Peters, W., Shiga, Y.
P., Thoning, K., van der Velde, I. R., van Leeuwen, T. T., Yadav, V. and Diffenbaugh, N. S.: Regional atmospheric CO2
inversion reveals seasonal and geographic differences in Amazon net biome exchange, Glob. Chang. Biol., 34273443, 5
doi:10.1111/gcb.13305, 2016.
Allan, D. W.: Statistics of Atomic Frequency Standards, Proc. IEEE, 54(2), 221230, doi:10.1109/PROC.1966.4634, 1966.
Allan, D. W.: Time and frequency (time-domain) characterization estimation and prediction of precision clocks and
oscillators, IEEE Trans. Ultrason. Ferroelectr., 34(6), 647654, 1987.
Andrews, A. E., Kofler, J. D., Trudeau, M. E., Williams, J. C., Neff, D. H., Masarie, K. A., Chao, D. Y., Kitzis, D. R., 10
Novelli, P. C., Zhao, C. L., Dlugokencky, E. J., Lang, P. M., Crotwell, M. J., Fischer, M. L., Parker, M. J., Lee, J. T.,
Baumann, D. D., Desai, A. R., Stanier, C. O., De Wekker, S. F. J., Wolfe, D. E., Munger, J. W. and Tans, P. P.: CO2, CO,
and CH4 measurements from tall towers in the NOAA Earth System Research Laboratory’s Global Greenhouse Gas
Reference Network: instrumentation, uncertainty analysis, and recommendations for future high-accuracy greenhouse gas
monitoring efforts, Atmos. Meas. Tech., 7(2), 647687, doi:10.5194/amt-7-647-2014, 2014. 15
Angevine, W. M., Eddington, L., Durkee, K., Fairall, C., Bianco, L. and Brioude, J.: Meteorological model evaluation for
CalNex 2010, Mon. Weather Rev., 120530140005004, doi:10.1175/MWR-D-12-00042.1, 2012.
Bréon, F. M., Broquet, G., Puygrenier, V., Chevallier, F., Xueref-Remy, I., Ramonet, M., Dieudonné, E., Lopez, M.,
Schmidt, M., Perrussel, O. and Ciais, P.: An attempt at estimating Paris area CO2 emissions from atmospheric concentration
measurements, Atmos. Chem. Phys., 15(4), 17071724, doi:10.5194/acp-15-1707-2015, 2015. 20
Brioude, J., Angevine, W. M., Ahmadov, R., Kim, S.-W., Evan, S., McKeen, S. a., Hsie, E.-Y., Frost, G. J., Neuman, J. a.,
Pollack, I. B., Peischl, J., Ryerson, T. B., Holloway, J., Brown, S. S., Nowak, J. B., Roberts, J. M., Wofsy, S. C., Santoni, G.
W., Oda, T. and Trainer, M.: Top-down estimate of surface flux in the Los Angeles Basin using a mesoscale inverse
modeling technique: assessing anthropogenic emissions of CO, NOx and CO2 and their impacts, Atmos. Chem. Phys., 13(7),
36613677, doi:10.5194/acp-13-3661-2013, 2013. 25
Conil, S. and Hall, A.: Local Modes of Atmospheric Variability: A Case Study of Southern California, J. Clim., 19, 4308
4325, 2006.
Conley, S., Franco, G., Faloona, I., Blake, D. R., Peischl, J. and Ryerson, T. B.: Methane emissions from the 2015 Aliso
Canyon blowout in Los Angeles, CA, Science (80-. )., 351(6279), 13171320, doi:10.1126/science.aaf2348, 2016.
Cui, Y. Y., Brioude, J., McKeen, S. A., Angevine, W. M., Kim, S.-W., Frost, G. J., Ahmadov, R., Peischl, J., Bousserez, N., 30
Liu, Z., Ryerson, T. B., Wofsy, S. C., Santoni, G. W., Kort, E. A., Fischer, M. L. and Trainer, M.: Top-down estimate of
methane emissions in California using a mesoscale inverse modeling technique: The South Coast Air Basin, J. Geophys.
Res. Atmos., 120(13), 66986711, doi:10.1002/2014JD023002, 2015.
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
c
Author(s) 2016. CC-BY 3.0 License.
33
Djuricin, S., Pataki, D. E. and Xu, X.: A comparison of tracer methods for quantifying CO2 sources in an urban region, J.
Geophys. Res., 115, D11303, doi:10.1029/2009JD012236, 2010.
Djuricin, S., Xu, X. and Pataki, D. E.: The radiocarbon composition of tree rings as a tracer of local fossil fuel emissions in
the Los Angeles basin: 1980-2008, J. Geophys. Res. Atmos., 117(12), 115, doi:10.1029/2011JD017284, 2012.
Dlugokencky, E. J.: Conversion of NOAA atmospheric dry air CH4 mole fractions to a gravimetrically prepared standard 5
scale, J. Geophys. Res., 110(D18), D18306, doi:10.1029/2005JD006035, 2005.
Dlugokencky, E. J., Lang, P. M. and Masade, K. A.: The growth rate and distribution of atmospheric methane, , 99(94),
1994.
Duren, R. M. and Miller, C. E.: Measuring the carbon emissions of megacities, Nat. Clim. Chang., 2(8), 560562,
doi:10.1038/nclimate1629, 2012. 10
Etiope, G. and Ciccioli, P.: Earth’s degassing: A missing ethane and propane source, Science, 323, 478,
doi:10.1126/science.1165904, 2009.
Feng, S., Lauvaux, T., Newman, S., Rao, P., Ahmadov, R., Deng, A., Díaz-Isaac, L. I., Duren, R. M., Fischer, M. L., Gerbig,
C., Gurney, K. R., Huang, J., Jeong, S., Li, Z., Miller, C. E., O’Keeffe, D., Patarasuk, R., Sander, S. P., Song, Y., Wong, K.
W. and Yung, Y. L.: LA Megacity: a High-Resolution Land-Atmosphere Modelling System for Urban CO2 Emissions, 15
Atmos. Chem. Phys., 16, 90199045, doi:10.5194/acp-16-9019-2016, 2016.
Filges, A., Gerbig, C., Chen, H., Franke, H., Klaus, C. and Jordan, A.: The IAGOS-core greenhouse gas package: a
measurement system for continuous airborne observations of CO2, CH4, H2O and CO, Tellus B, 67, 27989,
doi:10.3402/tellusb.v67.27989, 2015.
Graven, H. D., Guilderson, T. P. and Keeling, R. F.: Observations of radiocarbon in CO2 at La Jolla, California, USA 199220
2007: Analysis of the long-term trend, J. Geophys. Res., 117(D2), D02302, doi:10.1029/2011JD016533, 2012.
Gurney, K. R., Mendoza, D. L., Zhou, Y., Fischer, M. L., Miller, C. C., Geethakumar, S. and de la Rue du Can, S.: High
Resolution Fossil Fuel Combustion CO2 Emission Fluxes for the United States, Environ. Sci. Technol., 43(14), 55355541,
doi:10.1021/es900806c, 2009.
Gurney, K. R., Razlivanov, I., Song, Y., Zhou, Y., Benes, B. and Abdul-Massih, M.: Quantification of Fossil Fuel CO2 25
Emissions on the Building/Street Scale for a Large U.S. City, Environ. Sci. Technol., 46, 1219412202,
doi:/10.1021/es3011282, 2012.
Gurney, K. R., Romero-Lankao, P., Seto, K. C., Hutyra, L. R., Duren, R. M., Kennedy, C., Grimm, N. B., Ehleringer, J. R.,
Marcotullio, P., Hughes, S., Pincetl, S., Chester, M. V., Runfola, D. M., Feddema, J. J. and Sperling, J.: Track urban
emissions on a human scale, Nature, 525(7568), 179–181, doi:10.1038/525179a, 2015. 30
Hopkins, F. M., Kort, E. A., Bush, S. E., Ehleringer, J. R., Lai, C.-T., Blake, D. R. and Randerson, J. T.: Spatial patterns and
source attribution of urban methane in the Los Angeles Basin, J. Geophys. Res. Atmos., 121, 24902507,
doi:10.1002/2015JD024429.Received, 2016.
Hsu, Y.-K., VanCuren, T., Park, S., Jakober, C., Herner, J., FitzGibbon, M., Blake, D. R. and Parrish, D. D.: Methane
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
c
Author(s) 2016. CC-BY 3.0 License.
34
emissions inventory verification in southern California, Atmos. Environ., 44(1), 17, doi:10.1016/j.atmosenv.2009.10.002,
2010.
Hutyra, L. R., Duren, R., Gurney, K. R., Grimm, N., Kort, E. a., Larson, E. and Shrestha, G.: Urbanization and the carbon
cycle: Current capabilities and research outlook from the natural sciences perspective, Earth’s Future, 2(10), 473495,
doi:10.1002/2014EF000255, 2014. 5
IEA: World Energy Outlook, Ch.8, 179-193, International Energy Agency, 2008.
Jacob, D. J., Crawford, J. H., Maring, H., Clarke, A. D., Dibb, J. E., Emmons, L. K., Ferrare, R. A., Hostetler, C. A., Russell,
P. B., Singh, H. B., Thompson, A. M., Shaw, G. E., McCauley, E., Pederson, J. R. and Fisher, J. A.: The arctic research of
the composition of the troposphere from aircraft and satellites (ARCTAS) mission: Design, execution, and first results,
Atmos. Chem. Phys., 10(11), 51915212, doi:10.5194/acp-10-5191-2010, 2010. 10
Jeong, S., Zhao, C., Andrews, A. E., Bianco, L., Wilczak, J. M. and Fischer, M. L.: Seasonal variation of CH4 emissions
from central California, J. Geophys. Res., 117(D11), D11306, doi:10.1029/2011JD016896, 2012.
Jeong, S., Hsu, Y. K., Andrews, A. E., Bianco, L., Vaca, P., Wilczak, J. M. and Fischer, M. L.: A multitower measurement
network estimate of California’s methane emissions, J. Geophys. Res. Atmos., 118(19), 1133911351,
doi:10.1002/jgrd.50854, 2013. 15
Kort, E. A., Frankenberg, C., Miller, C. E. and Oda, T.: Space-based observations of megacity carbon dioxide, Geophys.
Res. Lett., 39(17), L17806, doi:10.1029/2012GL052738, 2012.
Kort, E. A., Angevine, W. M., Duren, R. and Miller, C. E.: Surface observations for monitoring urban fossil fuel CO2
emissions: Minimum site location requirements for the Los Angeles megacity, J. Geophys. Res. Atmos., 118(3), 15771584,
doi:10.1002/jgrd.50135, 2013. 20
Ma, S. and Skou, E.: CO2 permeability in Nafio EW1100 at elevated temperature, Solid State Ionics, 178, 615619,
doi:10.1016/j.ssi.2007.01.030, 2007.
Masarie, K. A. and Tans, P. P.: Extension and integration of atmospheric carbon dioxide data into a globally consistent
measurement record, J. Geophys. Res., 100(D6), 1159311610, doi:10.1029/95JD00859, 1995.
McKain, K., Wofsy, S. C., Nehrkorn, T., Eluszkiewicz, J., Ehleringer, J. R. and Stephens, B. B.: Assessment of ground-25
based atmospheric observations for verification of greenhouse gas emissions from an urban region, Proc. Natl. Acad. Sci. U.
S. A., 109(22), 84238, doi:10.1073/pnas.1116645109, 2012.
McKain, K., Down, A., Raciti, S. M., Budney, J., Hutyra, L. R., Floerchinger, C., Herndon, S. C., Nehrkorn, T., Zahniser, M.
S., Jackson, R. B., Phillips, N. and Wofsy, S. C.: Methane emissions from natural gas infrastructure and use in the urban
region of Boston, Massachusetts., 2015. 30
Miller, J. B., Lehman, S., Verhulst, K. R., Miller, C., Duren, R., Newman, S., Higgs, J. and Sloop, C.: Initial Atmospheric
Fossil-fuel CO2 Estimates from the Los Angeles Megacity Project, in 43rd Global Monitoring Annual Conference, 2015
Program and Abstracts Booklet, NOAA Earth System Research Laboratory, Global Monitoring Division., 2015.
Nara, H., Tanimoto, H., Tohjima, Y., Mukai, H., Nojiri, Y., Katsumata, K. and Rella, C. W.: Effect of air composition (N2,
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
c
Author(s) 2016. CC-BY 3.0 License.
35
O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: Calibration and
measurement strategy, Atmos. Meas. Tech., 5(11), 26892701, doi:10.5194/amt-5-2689-2012, 2012.
Newman, S., Xu, X., Affek, H. P., Stolper, E. and Epstein, S.: Changes in mixing ratio and isotopic composition of CO2 in
urban air from the Los Angeles basin, California, between 1972 and 2003, J. Geophys. Res., 113(D23), D23304,
doi:10.1029/2008JD009999, 2008. 5
Newman, S., Jeong, S., Fischer, M. L., Xu, X., Haman, C. L., Lefer, B., Alvarez, S., Rappenglueck, B., Kort, E. A.,
Andrews, A. E., Peischl, J., Gurney, K. R., Miller, C. E. and Yung, Y. L.: Diurnal tracking of anthropogenic CO2 emissions
in the Los Angeles basin megacity during spring 2010, Atmos. Chem. Phys., 13(8), 43594372, doi:10.5194/acp-13-4359-
2013, 2013.
Newman, S., Xu, X., Gurney, K. R., Hsu, Y. K., Li, K. F., Jiang, X., Keeling, R., Feng, S., O’Keefe, D., Patarasuk, R., 10
Wong, K. W., Rao, P., Fischer, M. L. and Yung, Y. L.: Toward consistency between trends in bottom-up CO2 emissions and
top-down atmospheric measurements in the Los Angeles megacity, Atmos. Chem. Phys., 16(6), 38433863,
doi:10.5194/acp-16-3843-2016, 2016.
Pacala, S. W., Breidenich, C., Brewer, P. G., Fung, I., Gunson, M., Heddle, G., Law, B., Marland, G., Paustian, K., Prather,
M., Randerson, J. T., Tans, P. and Wofsy, S. C.: Verifying greenhouse gas emissions: methods to support international 15
climate agreements, 2011.
Peischl, J., Ryerson, T. B., Brioude, J., Aikin, K. C., Andrews, a. E., Atlas, E., Blake, D., Daube, B. C., de Gouw, J. A.,
Dlugokencky, E., Frost, G. J., Gentner, D. R., Gilman, J. B., Goldstein, A. H., Harley, R. A., Holloway, J. S., Kofler, J.,
Kuster, W. C., Lang, P. M., Novelli, P. C., Santoni, G. W., Trainer, M., Wofsy, S. C. and Parrish, D. D.: Quantifying sources
of methane using light alkanes in the Los Angeles basin, California, J. Geophys. Res. Atmos., 118(10), 49744990, 20
doi:10.1002/jgrd.50413, 2013.
Prasad, K., Bova, A., Whetstone, J. R. and Novakovskaia, E.: Greenhouse Gas Emissions and Dispersion: 1. Optimum
Placement of Gas Inlets on a Building Rooftop for the Measurements of Greenhouse Gas Concentration., 2013.
Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A, Harth, C., Salameh, P.,
O’Doherty, S., Wang, R. H., Porter, L. and Miller, B. R.: Evidence for substantial variations of atmospheric hydroxyl 25
radicals in the past two decades., Science, 292(5523), 18828, doi:10.1126/science.1058673, 2001.
Rahn, D. A. and Mitchell, C. J.: Diurnal Climatology of the Boundary Layer in Southern California Using AMDAR
Temperature and Wind Profiles, J. Appl. Meteorol. Climatol., 55(5), 11231137, doi:10.1175/JAMC-D-15-0234.1, 2016.
Rella, C. W., Chen, H., Andrews, A. E., Filges, A., Gerbig, C., Hatakka, J., Karion, A., Miles, N. L., Richardson, S. J.,
Steinbacher, M., Sweeney, C., Wastine, B. and Zellweger, C.: High accuracy measurements of dry mole fractions of carbon 30
dioxide and methane in humid air, Atmos. Meas. Tech., 6(3), 837860, doi:10.5194/amt-6-837-2013, 2013.
Richardson, S. J., Miles, N. L., Davis, K. J., Crosson, E. R., Rella, C. W. and Andrews, A. E.: Field testing of cavity ring-
down spectroscopy analyzers measuring carbon dioxide and water vapor, J. Atmos. Ocean. Technol., 29(3), 397406,
doi:10.1175/JTECH-D-11-00063.1, 2012.
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
c
Author(s) 2016. CC-BY 3.0 License.
36
Riley, W. J., Hsueh, D. Y., Randerson, J. T., Fischer, M. L., Hatch, J. G., Pataki, D. E., Wang, W. and Goulden, M. L.:
Where do fossil fuel carbon dioxide emissions from California go? An analysis based on radiocarbon observations and an
atmospheric transport model, J. Geophys. Res. Biogeosciences, 113, 116, doi:10.1029/2007JG000625, 2008.
Rolph, G.D., Real-time Environmental Applications and Display sYstem (READY). NOAA Air Resources Laboratory,
Silver Spring, MD, Website (http://ready.arl.noaa.gov), 2016. 5
Ruckstuhl, A. F., Henne, S., Reimann, S., Steinbacher, M., Vollmer, M. K., O’Doherty, S., Buchmann, B. and Hueglin, C.:
Robust extraction of baseline signal of atmospheric trace species using local regression, Atmos. Meas. Tech., 5(11), 2613
2624, doi:10.5194/amt-5-2613-2012, 2012.
Ryerson, T. B., Andrews, A. E., Angevine, W. M., Bates, T. S., Brock, C. A., Cairns, B., Cohen, R. C., Cooper, O. R., De
Gouw, J. A., Fehsenfeld, F. C., Ferrare, R. A., Fischer, M. L., Flagan, R. C., Goldstein, A. H., Hair, J. W., Hardesty, R. M., 10
Hostetler, C. A., Jimenez, J. L., Langford, A. O., McCauley, E., McKeen, S. A., Molina, L. T., Nenes, A., Oltmans, S. J.,
Parrish, D. D., Pederson, J. R., Pierce, R. B., Prather, K., Quinn, P. K., Seinfeld, J. H., Senff, C. J., Sorooshian, A., Stutz, J.,
Surratt, J. D., Trainer, M., Volkamer, R., Williams, E. J. and Wofsy, S. C.: The 2010 California Research at the Nexus of Air
Quality and Climate Change (CalNex) field study, J. Geophys. Res. Atmos., 118(11), 58305866, doi:10.1002/jgrd.50331,
2013. 15
Shusterman, A. A., Teige, V., Turner, A. J., Newman, C., Kim, J. and Cohen, R. C.: The BErkeley Atmospheric CO2
Observation Network: initial evaluation, , 123, doi:10.5194/acp-2016-530, 2016.
Stein, A. F., Draxler, R. R., Rolph, G. D., Stunder, B. J. B., Cohen, M. D. and Ngan, F.: NOAA’s HYSPLIT atmospheric
transport and dispersion modeling system, Bull. Am. Meteorol. Soc., 96(12), 20592077, doi:10.1175/BAMS-D-14-00110.1,
2015. 20
Thoning, K. W., Tans, P. P. and Komhyr, W. D.: Atmospheric carbon dioxide at Mauna Loa Observatory: 2. Analysis of the
NOAA GMCC data, 19741985, J. Geophys. Res., 94(D6), 8549, doi:10.1029/JD094iD06p08549, 1989.
Turnbull, J. C., Sweeney, C., Karion, A., Newberger, T., Lehman, S. J., Tans, P. P., Davis, K. J., Lauvaux, T., Miles, N. L.,
Richardson, S. J., Cambaliza, M. O., Shepson, P. B., Gurney, K., Patarasuk, R. and Razlivanov, I.: Toward quantification
and source sector identification of fossil fuel CO2 emissions from an urban area: Results from the INFLUX experiment, J. 25
Geophys. Res. Atmos., 120(1), 292312, doi:10.1002/2014JD022555, 2015.
United Nations: World Urbanization Prospects: The 2014 Revision, Highlights (ST/ESA/SER.A/352)., 2014.
Viatte, C., Lauvaux, T., Hedelius, J. K., Parker, H., Chen, J., Jones, T., Franklin, J. E., Deng, A. J., Gaudet, B., Verhulst, K.,
Duren, R., Wunch, D., Roehl, C., Dubey, M. K., Wofsy, S. and Wennberg, P. O.: Methane emissions from dairies in the Los
Angeles Basin, Atmos. Chem. Phys. Discuss., 147, doi:10.5194/acp-2016-281, 2016. 30
Ware, J., Kort, E. A., Decola, P. and Duren, R.: Aerosol lidar observations of atmospheric mixing in Los Angeles:
Climatology and implications for greenhouse gas observations, J. Geophys. Res. Atmos., 121(98629878), 117,
doi:10.1002/2016JD024953, 2016.
Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-850, 2016
Manuscript under review for journal Atmos. Chem. Phys.
Published: 4 October 2016
c
Author(s) 2016. CC-BY 3.0 License.